JPS6024819B2 - Azo dye containing a new diazo component - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a monoazo dye containing a novel diazo component for photography.

In particular, it relates to dye-releasing redox compound intermediates and releasing dyes for color diffusion transfer photography. More specifically, the present invention relates to intermediates for dye-releasing redox compounds and releasing dyes with improved transferability, fastness and hue. JP-A No. 48-13 No. 26, No. 49-1
No. 14424, No. 49-126, No. 1, No. 49-126
No. 332, No. 50-115528, No. 51-1043
No. 43, U.S. Patent No. 3,92 & 312, U.S. Patent No. 3,931
, No. 144, No. 3,954,476, and “Research Disclo.”
sme" Ken 13024 (1975) describes a color diffusion transfer image forming method using dye-releasing redox compounds.

Here, the "dye-releasing redox compound" is a compound in which a group called a redox core and a dye (including its precursor) moiety are bonded. This redox mother nucleus initially immobilizes this redox compound by the action of the ballast group bonded thereto, but due to the redox reaction under alkaline conditions, it splits itself and forms a compound containing a pigment moiety ( (hereinafter referred to as release dye). That is, when a sensitive material having a photosensitive halide emulsion layer combined with this redox compound is subjected to fujiko treatment and developed with an alkaline processing solution, the redox compound itself is oxidized depending on the amount of developed silver halide, and further The alkaline treatment solution splits the released dye into, for example, a non-diffusible quinone compound. As a result, the released dye diffuses into the image-receiving layer and provides a transferred image thereto. Examples of redox compounds that release yellow dyes include U.S. Pat. No. 3,928,312, “Research Disc.
There are those described in "losme" magazine 13024 (1975).

However, when using the dye-releasing redox compounds specifically described in these prior documents, the stability of the transferred dye is insufficient (for example, the lightfastness is insufficient, and the color does not change in bright light). Furthermore, there were technical problems such as insufficient transfer of the dye compound and slow transfer speed. Furthermore, JP-A-52-
No. 7727 describes an improved yellow dye-releasing redox compound, but subsequent research has revealed that the hue of the released dye compound varies greatly with pH.

Examples of redox compounds that release magenta dye include JP-A-50-115528 and JP-A-49-114424.
No. 3,932,38, U.S. Patent No. 3,931,1
There is one described in No. 44.

However, when using the magenta dye-releasing redox compounds specifically described in these prior documents, the stability of the transferred color image may be insufficient (for example, the light fastness may be insufficient, or There were also technical problems such as the color image fading was also significant) and the transfer of the dye compound was insufficient.

For example, when talking about the fading of a magenta transferred color image,
When a polymeric acid (e.g., polyacrylic acid, a copolymer of acrylic acid and butyl acrylate, etc.) as disclosed in U.S. Pat. or butyl acrylate, etc.) are known to worsen the fading of transferred color images.

In particular, the residual butyl acrylate monomer greatly worsens the dark fading of magenta images obtained by the method of prior patents (for example, U.S. Pat. No. 3,932,38).
This was revealed in subsequent research. It is technically very difficult to suppress the amount of such residual monomer to an extent that does not affect the fastness of the image. Therefore, it is desired to develop a releasing dye that does not easily react with such monomers and a redox compound that releases the dye. The first object of the present invention is to provide a monoazo dye containing a novel diazo component for photography.

Second, there is the need to provide intermediate dye-releasing redox compounds that provide stable yellow and magenta dye images.

Thirdly, it is an object of the present invention to provide an intermediate for a redox compound releasing yellow and magenta dyes with good hues of releasing dyes.

Fourth, there is the need to provide a dye-releasing redox compound intermediate that provides yellow and magenta transferred images with virtually no hue change over a wide range of areas.

Fifth, it is an object of the present invention to provide an intermediate for a dye-releasing redox compound that has improved transferability of the dye compound. Sixthly, the present invention provides a monoazo dye that provides stable yellow and magenta dye images.

Seventhly, it is necessary to provide a photographic monoazo dye with good hue.

Eighthly, the present invention provides a photographic monoazo dye which shows virtually no change in hue over a wide pH range when dyed with a soot beam agent.

The above objects are achieved by a monoazo dye represented by the following general formula (1).

General formula: where RI is an alkylene group having 2 to 8 carbon atoms; R2 is an alkyl group having 1 to 8 carbon atoms: E is -0 days (however, EI and E2 may be the same or different, and each Hydrogen atom, alkyl group having 1 to 8 carbon atoms, aralkyl group having 7 to 15 carbon atoms, or 6 to 15 carbon atoms
represents an aryl group.

EI and E2 are connected directly or through an oxygen atom to form 5-
A 6 true saturated heterocycle may also be formed. ) or a halogen atom consisting of a chlorine atom, a bromine atom, and a fluorine atom; D represents a group represented by the following general formula (b) or (m).

However, Q is a cyano group, a trifluoromethyl group, or a carbamoyl group represented by 1CONR3R4 (where R3 represents a hydrogen atom or an alkyl group, and R4 represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group).

R3 and R4 may be linked directly or via an oxygen atom to form a ring); M is a hydrogen atom, an alkyl group, a sulfamoyl group represented by -S02NR3R4 (R3 and R4 have the same meanings as above); ), a group represented by -COOR5 (R5 represents an alkyl group, a phenyl group, or a substituted phenyl group), or a halogen atom.

However, QI is a hydrogen atom, a halogen atom, a sulfamoyl group represented by -S02NR3R4 (here, R3 and R4 have the same meanings as in the case of formula 0), -S02R6 (R6 represents an alkyl group or a pendyl group), a carboxyl group. represents a group, -COOR5 (R5 has the same meaning as formula D), or -CONR3R4 (R3, R4 have the same meaning as in formula 0); Q2 is in the 5th or 8th position relative to the O symbol; , hydroxyl group or -NH-COR4 or -NHSQ
R4 (in the formula, R4 has the same meaning as in formula 0 except that a hydrogen atom is excluded) represents a group.

To explain in more detail, carbon number 2 to 8 represented by RI
The alkylene group may be linear or branched (however, branched alkylene groups that form an acetal bond are not included).

Particularly preferred examples of RI include a direct mirror alkylene group represented by 1 (C) p- (where p is an integer of 2 to 4);
Examples include branched alkylene groups having 3 to 4 carbon atoms such as -CH(C&)CH2- (excluding those forming an acetal bond).

It is particularly advantageous if the RI is -CQC day 2 due to the availability of raw materials. When RI is a methylene group, it becomes an acetal bond like 10-CH21○-R2,
It is undesirable because it is chemically unstable (especially in acidic conditions) and decomposes during the synthesis process. For the same reason, the case where two oxygen atoms of the -○-RI-○-R2 group are bonded to the same carbon atom in RI (acetal bond) is not preferred. an alkyl group represented by R2 (
Includes unsubstituted and substituted alkyl groups. The same applies hereinafter), the alkyl group which may be straight or branched means an unsubstituted alkyl group and a substituted alkyl group. (The same applies hereinafter) R2 is preferably an unsubstituted alkyl group from the viewpoint of synthesis, and particularly preferred examples thereof include a straight or branched alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, n-propyl group). group, isopropyl group, n-butyl group, etc.). From a synthetic point of view, it is particularly preferred if R2 is a straight-chain alkyl group having 1 to 4 carbon atoms, especially a methyl and ethyl group.

When E is -OH, formula (1) represents a monoazo dye containing a sulfonic acid group.

In this case, the sulfonic acid groups may form salts. E is , then equation (1) becomes Represents a monoazo dye containing a sulfonamide group.

The alkyl group represented by EI or E2 may be straight, branched, or cyclic, and preferably has 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl. group, isobutyl group, sec
-butyl group, t-butyl group, t-pentyl group, cyclobentyl group, cyclohexyl group, cyclooctyl group, and other unsubstituted alkyl groups. In addition, these alkyl groups include a hydroxyl group, an alkoxy group (having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms), and an aryloxy group (having 6 to 10 carbon atoms).
, a substituted alkyl group substituted with a halogen atom, a carboxyl group, a sulfo group, or the like. EI or E2
The aralkyl group represented by is preferably one having 7 to 10 carbon atoms, and includes a benzyl group (alkoxy group, hydroxy group,
may be substituted with methylenedioxy group, etc.), Q
- and 6-phenethyl groups are representative.

The aryl group represented by EI or E2 has 6 to 1 carbon atoms.
A typical example is a phenyl group (which may be substituted with a halogen atom, an alkyl group, an alkoxy group, an acylamino group, a carpoxyl group, a sulfo group, etc.).

A typical example of a case where EI and E2 are connected directly or via an oxygen atom is a 5- to 6-membered saturated heterocyclic residue represented by .

Among the above, in the case of a releasing dye released from a dye-releasing redox compound, EI=E2=day is most preferred.

When E is a halogen atom, formula (1) represents a monoazo dye containing a sulfonyl halide group. As the halogen atom represented by E, a chlorine atom is particularly preferable in terms of synthesis. As a yellow dye, D has the above general formula (
To explain in more detail, in the general formula (0), in the case of a carbamyl group represented by the formula -CO-NR3R4, R3 is a hydrogen atom or a group having 1 to 1 carbon atoms. An alkyl group having 8 (more preferably 1 to 4 carbon atoms) is preferable, and this alkyl group may be substituted with a cyano group, an alkoxy group, a hydroxyl group, a carpoxyl group, a sulfo group, or the like.

R4 is hydrogen, an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms) (which may be substituted with a substituent as described below), benzyl group, phenyl group, or 6 carbon atoms. ~9 substituted phenyl groups are preferred. Also, R3 and R
4 may be bonded directly or via oxygen to form a 5- to 6-membered ring. Among these, the case where ■R3 and R4 are both hydrogen atoms, or ■at least one of R3 and R4 is a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms is cheap and easily available. It is particularly preferable from the viewpoint of excellent transferability and transferability. As Q, a cyano group is particularly preferable from the viewpoint of fastness of the transfer dye compound. The alkyl group represented by M is preferably one in which the alkyl moiety has 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms);
It may be substituted with the substituents listed in the case of 5.

When M is a sulfamoyl group represented by the formula -SQNR3R4, the preferable or particularly preferable one of R3 and R4 is that the group to be obtained is previously represented by the formula -CONR3R
It is exactly the same as what was mentioned about the carbamoyl group of 4.

Preferred examples of R5 include an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms) (which may be substituted with a substituent as described below), a phenyl group, and an alkyl group having 6 to 9 carbon atoms. Examples include substituted phenyl groups.

The alkyl groups in R3 to R5 above may be substituted with a sia group, an alkoxy group, a hydroxyl group, a carboxyl group, a sulfo group, or the like.

The halogen atom represented by M is particularly preferably a chlorine atom. Examples of substituents for the substituted phenyl group in R4 to R5 include a hydroxy group, a halogen atom, a carboxy group, a sulfo group, a sulfamoyl group, an alkyl group, an alkoxy group, and the like.

As a magenta dye, D is a group represented by the above general formula (machi), and to explain in more detail, general formula (m)
In this case, the alkyl group represented by R6 is the above-mentioned R3-
It may be substituted with the substituent mentioned in the case of R5.

Particularly preferred compounds of the present invention are those represented by the formula (1) as shown below: RI is -C&1CH2-; R2 is a straight chain or branched alkyl group having 1 to 4 carbon atoms; ; D is represented by formula (b) or (m).

More preferably, the expression in the formula (1) is as shown below: RI is C ratio - CH2 - R2 is a chain alkyl group having 1 to 4 carbon atoms: ○ is the formula (
0) or (m).

More preferably, the expression in the formula (1) is as shown below: RI is 1C ratio CH2; R2 is a linear unsubstituted alkyl group having 1 to 4 carbon atoms; ○
is represented by the formula (0) or (machi); E is 10H, 1NH2 or CI.

More preferably, the representation in formula (1) is as shown below: RI is C-CH2; R2 is a methyl group or an ethyl group.

D is represented by formula (0) or (m); E is 10H, 1NH2 or CI.

Specific examples of the dyes of the present invention are shown below. Compound A-1 (However, R2=C is E=OH) Compound B-1 In the formula of compound A-1, R2=CH3
, E=CI 〃 C-1 In the formula of compound A-1, R2=CH3, E=NH2 〃 A-2 In the formula of compound A-1, R2=C2 5, E=OH 〃 B-2 Compound A-1 In the formula of R2=C25, E=CI 〃 C-2 In the formula of compound A-1, R2=C25, E=NH2 Compound A-3 (E=OH) Compound B-3 Compound A-3 In the formula of E=CI 〃 C-3 In the formula of compound A-3 E=N ratio Compound A-4 (However, E=OH Compound B-4 In the formula of compound A-4 E=CI 〃 C-4 Compound A In the formula of compound A-5, E=N ratio Compound A-5 (however, E=OH) Compound B-5 In the formula of compound A-5, E=CI 〃 C-5 In the formula of compound A-5, E=N ratio Compound A -6 (however, E=OH) Compound B-6 In the formula of compound A-6, E=CI 〃 C-6 In the formula of compound A-6, E=N is compound A-7 (however, E=OH) Compound 8- 7 In the formula of compound A-7, E=CI 〃 C-7 In the formula of compound A-7, E=N ratio Compound A-8 (however, E=OH) Compound B-8 In the formula of compound A-8, E=CI C-8 E=N ratio in the formula of compound A-8 Compound A-1 (however, E=OH) Compound B-1 E=CI in the formula of compound A'-1
C'-1 In the formula of compound A'-1, E=N ratio Compound A'-2 (however, E=OH) Compound B-2 In the formula of compound A'-2, E=CI〃
C'-2 In the formula of compound A'-2, E=N ratio Compound A'-3 (however, E=OH) Compound B-3 In the formula of compound A'-3, E=CI〃
C'-3 In the formula of compound A'-3, E=N compound A'-4 (however, E=OH) Compound B'-4 In the formula of compound A'-4, C'
-4 In the formula of compound A'-4, E=N ratio Compound A'
-5 (E=OH) Compound B-5 In the formula of compound A'-5, C'-
5 In the formula of compound A'-5, E=N ratio Compound A'-
6 (However, E=OH) Compound B'-6 In the formula of compound A'-6, C'
-6 In the formula of compound A'-6, E=N Buddha compound A'
-7 (However, E=OH) Compound B-7 In the formula of compound A'-7, E=CI〃
C'-7 In the formula of compound A'-7, E=N & Compound A-8 (however, E=OH) Compound B'-8 In the formula of compound A'-8, E=CI
〃 C'-8 In the formula of compound A'-8, E=NQ Compound C-9 Compound C'-9 Compound C-10 As a method for synthesizing the diazo component effective for synthesizing the compound of the present invention, for example, the following formula There is a method.

Needless to say, this diazo component is E=O in formula (1).
It is effective as an intermediate for the synthesis of H compounds (or salts thereof). In the formula, Hal represents a halogen atom (especially preferably a chlorine atom), and RI and R2 have the same meanings as in formula (1).

First, as a method for synthesizing E from compound D, R2-
A reaction using an alkoxide 0-RI-ONa (wherein R2 and RI have the same meanings as in formula (1)) can be mentioned. This alkoxide can be obtained by treating alcohol R2-○-RI-OH with metallic sodium, sodium hydride, or the like. Excess R2○-
Although RI-OH may be distilled off and R2-○-RI-ONa isolated for use, usually R2-○-RI-ONa is
It is preferable to use the 21○-RI-OH solution as it is. R2-RIONa per mole of compound of formula D
is about 1 mol to about 50 mol, preferably about 1 mol to about 10 mol
It is desirable to use moles, more preferably about 1 mole to about 3 moles. The temperature of the reaction is about 120℃ to about 150℃,
The temperature is preferably 000 to 100°C, more preferably 3 to 8 yo to suppress by-products. Compound E
In a second synthesis method, the compound of formula ○ is converted into R2-○
There is a method of treatment with sodium hydroxide or potassium hydroxide in the presence of manganese dioxide in -RI-OH.
In this case, sodium hydroxide is particularly preferred. R
About 100 to about 50 (preferably about 300 to about 5, especially about 400 to about 2) of 21○-RI-OH
and treated with about 1 mole to about 50 moles (preferably about 1 mole to about 10 moles, especially about 1 mole to about 3 moles) of sodium hydroxide.

At this time, it is desirable to maintain the reaction temperature at about 0°C to about 15°C (preferably 0°C to 100°C, particularly 3°C to 85°C). As a third method of synthesis of compound E, a compound of formula D is prepared in R2-○-RI-OH by sodium silicate (Na20.nSi02, n=about 1 to about 5, preferably about 1 to about 3 ) in the presence of sodium hydroxide or potassium hydroxide. In this case, treatment with sodium hydroxide is preferred. 1 mole of compound of formula D and about 1 mole of sodium silicate to about 100 moles (preferably about 1 mole of sodium silicate)
from about 50 females, more preferably from about 3 females to about 10 females, and from about 100 females to about 50 females (preferably from about 300 females to about 5 females, more preferably from about 300 females to about 5 females) of R2-RI-OH. is about 40
0 to about 2 moles) and treated with about 1 mole to about 50 moles (preferably about 1 mole to about 10 moles, more preferably about 1 mole to about 3 moles) of sodium hydroxide. The reaction temperature is about 0°C to about 150qo (preferably 0°C to 100qo
qo, more preferably from 30 pm to 85 qo). After the reaction solution obtained by the above three methods is filtered to remove insoluble matter, the quenching solution is mixed with a poor solution (e.g., an alcoholic solvent such as inpropyl alcohol or n-butanol; an aromatic hydrocarbon solvent such as toluene). (solvent; ester solvent such as ethyl acetate) to crystallize the compound of formula E. If necessary, further purification operations such as recrystallization may be added according to conventional methods. In addition, the compound of formula E can be obtained by sulfonating p-(R2101RI-○chiC61N02 according to the method described in Chemical Abstracts cited above.

It is also possible to chlorosulfonylate p-(R2-○-RI-0)-C6 ratio-N02 with chlorosulfonic acid; probably via a number of compounds). L.F. Fieser, “Experimen- tal Chemistry”
3rd edition, 2nd edition
Chapter 6, D.C.HeathandCo. 1955 (reprinted edition, Maruzen 1956) describes a general formula and method for obtaining sulfonyl chloride using chlorosulfonic acid. When this sulfonyl chloride (2-alkoxyalkoxy-5-nitrobenzenesulfonyl chloride) is heated to reflux in methanol, the corresponding sulfonic acid (formula E
In this step, a methanol solution is obtained in which Na is replaced by day. If this is treated with potassium acetate, calcium hydroxide, barium hydroxide, pyridine, etc., in formula E, instead of Na, K, Ca211/2, mother211/2, etc.
Each day, a unique compound can be obtained. Calcium salts and barium salts can also be synthesized from the corresponding sodium salts by utilizing the difference in solubility in water. These derivatives of compound E are useful as synthetic intermediates, but in view of cost and synthetic advantages, it is preferable to use compound E itself as an intermediate. Methods for obtaining compound F by reducing the nitro group of the compound represented by formula E include reduction with iron powder, catalytic hydrogenation (Raney nickel or palladium-carbon catalyst), hydrazine reduction (Raney nickel, palladium-carbon or activated carbon catalyst) ) are typical examples.

Other methods for converting a nitro group into an amino group by reducing the nitro group include, for example, "R.B. Wagner" (R.B. Wagner)
er) and “H.D.ZOO” (日.D.ZOO
K) “Synthetic Organic Chemistry” (
Chapter 24, pages 654-657 (John Wiley, N.
ewYork, 1953), “Organic Functional Group Preparations” by S.R. Sandler and W. Karo
c F Hada ccio Misaki I GroupPreparati
ons) Chapter 13 339-345 (AcademicP
These methods are also effective for synthesizing the compounds of the present invention.

As an example of a method for obtaining compound F by reducing the nitro group of the compound represented by formula E, a reduction method using iron powder will be described below.

About 1 mol to about 100 mol, preferably about 1 mol to about 50 mol, more preferably about 1 mol of iron powder (preferably commercially available reduced iron, etc.) per 1 mol of the compound represented by formula E.
Moles to about 10 moles are used. The solvent for this reduction reaction is water and alcohols (methanol, ethanol,
Preferred are methoxycetal/- and the like. It is also possible to use a mixture of these solvents. Furthermore, a small amount of ammonium chloride (about 1/100 to about 1/10, preferably about 1/100 of the weight of the compound of formula E) is added as a reaction initiator.
~about 1/20) is desirable. The temperature of the above reaction is about 30°C to about 150qo, preferably about 50qo
It is desirable to keep it at ~100oo. The reaction solution thus obtained is passed through a furnace to remove insoluble matter, and then the solution is poured into a poor solvent (such as inpropyl alcohol) to precipitate the sodium salt of the compound represented by formula F. be able to. Further, by neutralizing the above-mentioned filtered reaction solution with concentrated hydrochloric acid, a compound represented by formula F can be obtained as an inner salt. A typical synthesis example of compound F will be described in detail below. Synthesis Example 1 Synthesis of sodium 2-(2-methoxyethoxy)-5-nitrobenzenesulfonate (Method 1) 7.3 g of sodium hydride (50% liquid paraffin suspension) in 300' of 2-methoxychetanol 1 in the form of
55 g of sodium 2-chloro-5-nitrobenzene-sulfonate was added to the sodium-2-methoxyethylate solution prepared by adding 4.6 g of 2-chloro-5-nitrobenzene-sulfonate.

The reaction mixture was heated in a hot water oven at 80-85°C for 3 times. After passing through a thermal oven, 1.5 volumes of inpropyl alcohol was added to the mother liquor for crystallization. The precipitated crystals were collected in a furnace and washed with inpropyl alcohol 100 Z. Yield 5%
, m. p. 2 papers - 23900. (Method 2) Sodium 2-chloro-5nitrobenzenesulfonate5. Shigeru, manganese dioxide 0. Arm, 2-methoxychetanol 15'
, mix 1 part of water and 09 parts of sodium hydroxide;
I worshiped the lights for 40 minutes at 5qo.

After cooling, insoluble matter was removed from the furnace, and the furnace solution was poured onto 100% inpropyl alcohol. The precipitated crystals are collected in a furnace,
Sodium 2-(2-methoxyethoxy)-5-nitrobenzenesulfonate4. I got a chick. m. p. 2 total - 23
Tsubo C. It gave the same infrared absorption spectrum as the compound obtained by method 1. (Method 3) Sodium silicate (
Na20.nSi02: n=approximately 3)0. Using a mallet, by exactly the same treatment, 2-(2-methoxychetoxy)-
Sodium 5-nitrobenzenesulfonate4. I got a chick.

(The same results as above were obtained using Na20/nSi02 with n=about 1, about 2, or about 2.5.) The same infrared absorption spectrum as the compound obtained in method 1 was obtained. Gave. Synthesis Example 2 Synthesis of sodium 2-(2-ethoxyethoxy)-5-nitrobenzenesulfonate 7. Paper sodium hydride (50% suspended in liquid paraffin).

14. In the form of turbidity. g) Sodium 2 prepared by adding
- Five sides of sodium 2-chloro-5-nitrobenzenesulfonate were added to the ethoxycetylate solution. The reaction mixture was kept at 80-85°C and heated for 3 minutes.
After the reaction is completed, after separating the impurities from the furnace, 1.
5 My ethyl cellosolve was washed away. 300% of inpropyl alcohol was added to the concentrated solution and cooled on ice. After separating the precipitated crystals in a furnace, inpropyl alcohol 100 [
It was washed and air dried. Yield 3 rounds, m. p. 248-2
49℃ or higher. In methods 2) and 3) of Synthesis Example 1,
The same compound was obtained using 2-ethoxyethanol instead of 2-methoxyethanol. Synthesis Example 3 Synthesis of sodium 2-(2-propoxyethoxy)-5-nitrobenzenesulfonate Sodium 2-chloro-5nitrobenzenesulfonate 26. Female, sodium silicate (Na20/nSi02: n=approx. 3)5. Suspend the female on 2-> propoxyethanol 120 and worship it while doing rope worship.
Sodium hydroxide5. A solution of female dissolved in 5 parts of water is 1 part
The mixture was added dropwise at 690° C. over 0 minutes.

After the dropwise addition was completed, the solution was poured at 65° C. for 3 hours, and then the insoluble matter was removed in a suction oven. When the furnace liquid was left to stand, a solid precipitated, so it was removed from the furnace and the furnace liquid was concentrated and dried. Add 100% ethanol to the residue.
When it was added, it crystallized and was removed from the furnace. After washing with inpropyl alcohol, it was dried at 50°C. Yield 14.
1 g, once melted at a melting point of 70 to 74 qo, then about 130 qo
It solidified at ℃, and when the temperature was further increased, it melted again at a melting point of 206 to 20 tsubo○. Synthesis Example 4 Synthesis of Sodium 2-(2-Butoxyethoxy)-5-nitrobenzenesulfonate The same procedure was carried out using ethylene glycol monobutyl ether instead of 2-methoxyshetanol in Synthesis Example 1 (Method 2). Work-up gave the title compound.

m. p. 104-10600. A specific synthesis example of compound (1) of the present invention will be described in detail below.

Synthesis example 55-amino-2-(2-methoxyethoxy)
Synthesis of sodium salt of benzenesulfonic acid Mixture of sodium 2-(2-methoxyshetoxy)-5nitrobenzenesulfonate obtained in Synthesis Example 1, 3 parts of reduced iron, 0.6 parts of ammonium chloride, and 60 parts of water. solution to 80-8
I kept it at YO temperature and heated it for 2 hours.

After the reaction was completed, the unmelted material was separated from the furnace, and 200% of inpropyl alcohol was added to the furnace solution, which was then cooled on ice. The precipitated crystals were collected in a furnace, washed with 50% of inpropyl alcohol, and air-dried. Yield 23&m. p. 250qC or higher Synthesis Example 6 Synthesis of 5-amino-2-(2-methoxyethoxy)benzenesulfonic acid Sodium 2-(2-methoxyethoxy)-5nitrobenzenesulfonate 2 obtained in Synthesis Example 1
Female, 1 leg of reduced iron, 0 ammonium chloride. Add a mixed solution of 40 parts inpropyl alcohol, and 40 parts water to 7 parts.
At the age of 70, I prayed for the 9th time.

After the reaction is complete, insoluble materials are separated from the furnace and concentrated hydrochloric acid (36%) is added to the furnace liquid.
Added 20'. The precipitated crystals were collected in a furnace, washed with 50% of inpropyl alcohol, and air-dried. Yield: 19
．． 6g m. P. :286-289q0 Synthesis Example 7 Synthesis of 5-amino-2-(2-ethoxyethoxy)benzenesulfonic acid Sodium 2-(2-ethoxyethoxy)-5nitrobenzenesulfonate 1 obtained in Synthesis Example 2
0 & reduced ferric acid, ammonium chloride 0. A mixed solution of 20 parts of inpropyl alcohol, and 20 parts of water.
I worshiped my husband for 2 hours at 0.

After the reaction is complete, insoluble materials are separated from the furnace and concentrated hydrochloric acid (36%) is added to the furnace liquid.
Added 10'. The precipitated crystals were collected in a furnace, washed with 30% of inpropyl alcohol, and air-dried. Yield: 7.
Ship m. P. :278-28pu○ Synthesis Example 8 Synthesis of 5-amino-2-(2-propoxyethoxy)benzenesulfonic acid Sodium 2-(2-propoxyethoxy)-5-nitrobenzenesulfonate obtained in Synthesis Example 3, reduced Tetsuji, ammonium chloride 0. He, 20 liters of inpropyl alcohol, and 20 ounces of water, 77 g
I worshiped the lights for 2 hours at 0.

After the reaction is complete, remove the insoluble matter. …Separate the Sagi furnace, add concentrated hydrochloric acid (3
6%) 10 sides were added and cooled. The precipitated crystals were taken up in a furnace and air-dried. Yield: 7.1g m. p. 287-29 p○ The following method is available as a method for synthesizing the diazo component that is effective for synthesizing the compound of the present invention.

This diazo component is a compound of formula (1). It is effective as a synthetic intermediate.

However, R1, R2, E1, and E2 have the same meanings as in formula (1), and Hal represents a halogen atom (preferably a chlorine atom).

To convert the compound of formula (E) to compound Hal=cl of formula (G), as a chlorinating agent, phosphorus oxychloride P○c13,
Thionyl chloride S0c12, or phosphorus pentachloride Pc15,
Preferably, chlorosulfonic acid or the like is used.

At this time, it is desirable to carry out the reaction in the presence of a carboxylic acid amide such as N,N-dimethylacetamide, N,N-dimethylformamide or N-methylpyrrolidone. A compound of formula (G) can be reacted with an amine called HNEIE2 to obtain a compound.

In the case of HNEIE2, ammonia, alkylamine, dialkylamine, etc., the compound can be obtained by using about 2 mol of HNEIE2 per 1 mol of the compound of formula (G). However, the compound of stop (G) and H
In the condensation reaction of NEIE2, it is desirable to use a basic substance as a deoxidizing agent. Examples of such basic substances include alkali metal or alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc.), aliphatic amines (e.g., triethylamine, etc.), aromatic Amines (e.g. N
. (1,6
-diazabicyclo[4,3,0]nonene-51;1,8
-Diazabicyclo[5,4,0]Untesene-7, etc.)
can be given. Representative examples of reduction reactions to obtain the compound of formula (J) include reduction with iron powder, catalytic hydrogenation (Raney nickel or palladium-carbon catalyst), and hydrazine reduction (Raney nickel, palladium carbon or activated carbon catalyst). be.

Reduction with iron powder has already been described in detail in the synthesis of the compound of formula (F), but it is also effective in the synthesis of the compound of formula (J). A representative synthesis example of Compound J will be described in detail below.

Synthesis Example 9 Synthesis of 5-amino-2-(2-methoxyethoxy)benzenesulfonamide'a) Synthesis of 2-(2-methoxyethoxy)-5-nitrobenzenesulfonyl chloride 2-(2-methoxyethoxy) obtained in Synthesis 1 59 g of sodium (toxy)-5-nitrobenzenesulfonate was added to a mixture of 200' of acetone and 75' of oquine phosphorus chloride.

75 ml of dimethylacetamide was added dropwise while stirring, and the reaction mixture was maintained at 30-40°C. After dropping, the solution was left to stand until it cooled to room temperature. The reaction mixture was poured into 600 ml of ice water, heated for 30 minutes, and the precipitated crystals were collected.

After washing with 100ml of water, it was air-dried. Yield: 5 m. p
．． 74-74.5ko0.

{b) Synthesis of 2-(2-methoxyethoxy)-5nitrobenzenesulfonamide
2-Methoxyshethoxy)-5nitrobenzenesulfonyl chloride*45 was dissolved in 2.3 liters of acetone, and 28% aqueous ammonia 455 quarts was added dropwise thereto in an amount of 50 qo or less.

I left it to cool for an hour and worshiped it.

The reaction solution was poured into a mixture of 300 parts of 35% hydrochloric acid and 5 parts of water. The precipitated crystals were taken out in a furnace and 21 of 40 foundations (
2-methoxyshethoxy)-5nitrobenzenesulfonamide was obtained. m. p. 125-130)○{c) 5
-Synthetic iron powder 41 of amino-2-(2-methoxyethoxy)benzenesulfonamide, 2-propanol 3Z,
Mix 9.7 g of ammonium chloride and 300 g of water,
2-(2-methoxyethoxy)-5nitrobenzenesulfonamide 40 synthesized in [bl] was added.

After 6 hours and 30 minutes of candle worship at an internal temperature of 770 on a steam bath, it was passed through a heat oven. When the furnace liquid was cooled, crystals precipitated and were collected. Yield 33 females m. p. 133-135qo To obtain a compound of formula (1) (where E=OH), diazo component F is diazotized and is represented by D (D is synonymous with formula (1)).

Coupling with a compound (coupler or coupling component): (where R1, R2, and D have the same meanings as in formula (1)) Diazotization of compound F can be performed, for example, as described in Yutaka Hosoda, "Shinchikuri Kagaku," Gihodo (1963) 114- p. 120, Hiroshi Horiguchi, “Synthetic Dyes Ichizo Eishuppan (1970), 114-1
This can be done by the method described on page 24.

Among these, it is preferable to diazotize the diazo component F by a method usually called the reverse method (ReveRedme ratio od). In this method, diazo component FI, about 1 mole of sodium nitrate, and about 1 mole of sodium hydroxide (or other alkali or alkali metal hydroxide) are dissolved in water, and the mixture is cooled. Add to key acid water (e.g. dilute hydrochloric acid, dilute sulfuric acid, etc.).

The amounts of sodium nitrite and sodium hydroxide are preferably the above amounts, but may be added in excess. The solution of diazonium salt thus obtained contains about 1 mol of D-
A coupling reaction is carried out by mixing with an organic solvent, solution, or aqueous solution of a coupler (D is synonymous with formula (1)). The organic solvent for dissolving the coupler is preferably one that is miscible with water, such as alcohols (methanol, ethanol, 2-pro/gnol, methoxyethanol,
ethoxyethanol, etc.), carponamides (N, N
-dimethylamide, N,N-dimethylformamide, etc.), carboxylic acids (acetic acid, butionic acid, etc.) are preferred. Furthermore, D-day may be dissolved in these mixed solutions. Furthermore, D1 day may be used as an alkaline aqueous solution. During this coupling reaction, it is preferable to coexist a basic substance. Desirable basic substances include sodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and the like. Among couplers represented by D (where D is synonymous with formula (1)), formula (W)
Alternatively, those represented by formula (V) are preferred. (However, the symbol has the same meaning as formula (0)) (However, the symbol has the same meaning as formula (m)) The details of the coupling reaction will be described in the following specific example, but the above-mentioned book by Horiguchi, pp. 124-129, Japanese. E.
Fierz-David and L. “Fundamental Processes of Dichemistry” by Blan Same
Fundamenne I PrMess of D
yeChemisWry” InterReience Pu
blishers Inc. , New York (194
9), pp. 239-297, K. Ve skin ata
“The Chemistry of Synthetic Dice” by Raman “The Chemistry of S
``Inthetic Dyes'' Academic Pr.
ess Inc. , New York (1952), No. 1
I will also mention the information in Chapter 1 as it may be helpful.

Synthesis example 10 3-cyano-4-[4-(2-methoxyethoxy)-5
Synthesis of -sulfophenylazo]-1-phenyl-5-pyrazolone (compound A-1) Sodium hydroxide8. 5-amino-2-(2-methoxyethoxy)benzenesulfonic acid in a solution of 200 g of water and 49. and then add 13. Added thigh water solution (50% above).

Separately, a solution of 60 parts of concentrated hydrochloric acid and 400 parts of water was prepared, and the above solution was added dropwise to this at 5°C or lower. 3 below 5℃
The reaction was completed by bowing for 0 minutes. Separately sodium hydroxide16. For cough, prepare a solution of 200 g of water, 33.0 g of sodium acetate and 200 g of methanol, and add 3-cyano-
1-Fenyl-5-Pyrazolone 37. Add female, 10q
The diazo solution prepared above was added dropwise at a temperature of 0 or less.

After the dropwise addition was completed, the mixture was stirred for 30 minutes at a temperature below 100°C, and then stirred at room temperature for 1 hour. The precipitated crystals were collected in a furnace, washed with 200% acetone, and air-dried. Yield 52.0gm.
p. 263-265q○ Synthesis Example 11-13 Synthesis Example 10
The compounds shown in Table 1 were synthesized in the same manner as above.

Table 1 Synthesis Example 14 2-(N-te ratio-butylsulfamoyl)-4-[4
Synthesis of 1-(2-methoxyethoxy)-5-sulfophenylazo]-15-1-methanesulfonamide-1-naphthol (compound A'-4) Add 5-amino to a solution of Z of 1.7 of sodium hydroxide and 80 of water. -2-(2-methoxyethoxy)
Benzene sulfonic acid9. Add tether, and add sodium nitrite 2. Total aqueous solution (10 volumes) was added.

Separately, prepare a solution of 18 parts of concentrated hydrochloric acid and 70 parts of water, and
The above solution was added dropwise below. Thereafter, the reaction was completed by heating at 5° C. or lower for 30 minutes (preparation of diazo solution). Separately, prepare a mixed solution of 8.0 parts sodium hydroxide, 40 parts water, and 150 parts methyl alcohol, and add 14 parts of 2-t-butylsulfamoyl-5-methanesulfonamide-1 naphthol. The diazo solution prepared at 10° C. or lower was added dropwise.

After the addition is complete, keep it under a light for 30 minutes at below 0℃, and add 20% of concentrated hydrochloric acid.
added. The precipitated crystals were collected in a furnace and diluted with acetone 200 [
and air dried. Yield: 1 m. p. 215-22
0qo Synthesis Examples 15-24 The compounds shown in Table 2 were synthesized in the same manner as in Synthesis Example 14.

In order to obtain the compound of formula (1) in Table 2 (where E=halogen atom), the sulfonic acid group of the compound of formula (1) (where E=OH) may be replaced with a halogenosulfonyl group.

Since the case where E=cl is particularly preferred, this synthesis method will be described. For converting the sulfonic acid group of formula (1) into a chlorosulfonyl group, the chlorinating agent mentioned in the synthesis of compound G can be used. This reaction proceeds smoothly when a carboxylic acid amide such as N,N-dimethylacetamide, N,N-dimethylformamide or N-methylpyrrolidone is present. Although the required amount of the chlorinating agent is determined by stoichiometry, it is often desirable to use an excess of chlorinating agent (1.5 to 5, preferably 1.5 to 1 tones above the theoretical amount). In most cases, this reaction proceeds satisfactorily at room temperature (approximately 25°C).If the reaction is vigorous, it is possible to cool it to approximately 0°C.On the other hand, if the reaction is slow, pi 0 (preferably 26
Heating may be performed in a range of 0 to 100°C). Even when E is other halogen, E. Miiller Green “Hou
Weyls Meth's enderOrganis
henChemic” Volume X, pages 557-598 (1
955).

The synthesis of formula (1) (where E:cl) will be explained in detail in the following synthesis example.

Synthesis example 25 3-cyano 4-[4-(2-methoxyethoxy)-5
-chlorosulfonylphenylazo]-1-phenyl-5
-Synthesis of pyrazolone (compound B-1) 3-cyano-4-[(4-methoxyethoxy-5-
Sulfophenylazo]-1-phenyl-5-vilazolone 51.0 g, acetone 250 and phosphorus oxychloride 5
50% of N,N-dimethylacetamide was added dropwise to the mixed solution at 50% or less.

After dripping, the solution was kept for about 1 hour, and then 1.0 g of ice water was gradually poured into it. After separating the precipitated crystals in a furnace, the
It was washed and air dried. Yield 46. Foundation m. p. 181-1
8yo Synthesis Examples 26 to 31 The compounds shown in Table 3 were synthesized in the same manner as in Synthesis Example 25.

Table 3 Synthesis Example 30 2-(N-butylsulfamoyl)-4-[4
Synthesis of 1-(2-methoxyethoxy)-15-chlorosulfonylphenylazo]-15-methanesulfonamide 1-naphthol (Compound B-4) The 2-obtained in Synthesis Example 14 above
(tert-butylsulfamoyl)141 [41 (2
-methoxyethoxy)-5-sulfophenylazo]-5
- N in a mixed solution of 1 methanesulfonamide 1 naphthol, 100 similar to acetone, 20 phosphorus oxychloride,
20 minutes of N-dimethylacetamide was added dropwise at a temperature of 50 minutes or less.

After dripping, the lamp was held for an hour, and then slowly poured into 500 drops of ice water. The precipitated crystals were separated from the furnace, washed with 50% acetonitrile, and air-dried. Yield: 1 crabm. p. 148-153°C Synthesis Examples 31-39 In the same manner as Synthesis Example 30, the compounds shown in Table 4 were synthesized.

Table 4 To obtain a compound of formula (1) (where E=-NEIE2), diazo component J is diazotized and D-day (D is formula (1)
Coupling with a compound (referred to as a coupler or coupling component) represented by (synonymous with): (However,
(R1, R2, E1, E2, E, D are synonymous with formula (1)) The diazotization of compound J can be carried out, for example, as described in the aforementioned Hosoda book 114-
This can be carried out by the method described on page 120 and pages 114 to 124 of Horiguchi's book.

Among these, it is preferable to diazotize the diazo component J by a method called a direct method. In this method, JI moles of the diazo component are dissolved in cooled mineral acid water (eg, dilute hydrochloric acid, dilute sulfuric acid, etc.), and an aqueous solution of about 1 mole of sodium nitrite is added. The amount of sodium nitrite is preferably the above amount, but may be added in excess. However, if excessive amounts are added, it is necessary to add urea or sulfamine to decompose the remaining nitrous acid.
The diazo component J is a water-miscible solvent (e.g. methanol,
It may be dissolved in alcohols such as ethanol, methoxyethanol, and ethoxyethanol; carboxylic acids such as acetic acid and propionic acid. The diazonium salt thus obtained is coupled with about 1 mol of a coupler D-day (D is the same as in formula (1)). For the coupling method, please refer to the detailed description of the coupling with diazotized F on day ○. formula(
Another method for obtaining a compound of 1) (where E=-NEIE2) is a method of condensing formula (1) (where E=a halogen atom) with an amine HNEIE2.

This condensation reaction can be carried out in the same manner as described above in the section of the condensation reaction between formula (G) and HNEIE2. The synthesis of the compound of formula (1) (where E=-NEIE2) will be explained in detail in the following synthesis example. Synthesis example 40 3-cyano 4-[4-(2-methoxyethoxy)-5
-Synthesis of sulfamoylphenylazo 1-phenyl-5-pyrazolone (compound C-1) 5-amino-2-(2-methoxyethoxy)benzenesulfonamide synthesized in Synthesis Example 9'c- 24. Mix the thighs with 200 parts of water, 3
28 cm of 5% hydrochloric acid was added and the mixture was cooled to below 5°C.

Add 6.0% sodium nitrite to this mixture. A solution prepared by dissolving the binder in 80 parts of water was added dropwise over 18 minutes (0 to 500). The mixture was further heated at 0 to 5°C for 20 minutes (adjustment of diazo solution). Separately 3-cyano-1-phenyl-5-pyrazolone18. Dissolve the gunk in ethanol and add 2 parts of sodium acetate to 60' of water.
and cooled to 5°C.

The above diazo solution was added to this solution. The precipitated crystals were collected in a furnace and recrystallized from N,N-dimethylformamide methanol. Yield 31. Group Melting point: 210-210 Synthesis examples 41-46 The compounds shown in Table 5 were synthesized in the same manner as in Synthesis example 40.

Table 5 Synthesis Examples 47-54 The compounds shown in Table 6 were synthesized in the same manner as in Synthesis Example 40.

Table 6 Compounds of the present invention can be used as intermediates to synthesize dye-releasing redox compounds (hereinafter referred to as "DRR compounds") useful in color diffusion transfer methods.

Representative examples of DRR compounds include compounds represented by the following general formula (N). However, D has the same meaning as in formula (1); R, Rib has the same meaning as RI in formula (1); R, R2b has the same meaning as R2 in formula (1), and m is 0. or 1; Y is o- having a ballast group;
Or it represents a P-hydroxyarylsulfamoyl group. (In the following description, RI and R2 are R1a and Rib, and R21 and R2b, respectively, unless otherwise specified.
Described as meaning.

) The above general formula is characterized by the presence of a group -○-RI-○-R2 in the dye moiety (particularly the moiety that is derived from the diazo component).

The second feature is that this 10-RI-○-R2 group is located at the 4-position with respect to the azo group, and the 1S02NH- group (formula (W
), when m is 0, it is included in Y) is at the 3-position with respect to the azo group. It will be discussed later that this positional relationship has the effect of suppressing changes in hue due to pH. Thirdly -○-RI-○-R
It is important that 2 and Y are in an ortho positional relationship.
The reason for the improvement in transferability is thought to be that this strengthens the function of Y as a redox nucleus, making it possible to release the dye compound more effectively. The sulfamoyl group substituted with an o- or p-hydroxyaryl group having a ballast group, represented by Y, is preferably represented by general formula (V).

However, pith 11 represents a ballast group; T represents an atomic group necessary to complete a benzene nucleus or a naphthalene nucleus containing a substituted benzene nucleus or a substituted naphthalene nucleus; -NHS02
The - group in the formula occupies the o- or p-position relative to the hydroxyl group.

When T represents a naphthalene nucleus, Ball is attached to at least one ring of the naphthalene nucleus. Examples of the substituents bonded to the benzene nucleus or naphthalene nucleus include an alkyl group (preferably one having 1 to 7 carbon atoms) and a halogen atom (chlorine atom, etc.).

Further, a ring (for example, a 5- to 6-membered ring) may be fused to the benzene nucleus. The ballast group is an organic ballast group that can make the DRR compound non-diffusible even during development in an alkaline processing solution, and has 8 to 3 carbon atoms.
Preference is given to groups containing up to 2 hydrophobic groups.

Such an organic ballast group can be attached to the dye-releasing redox compound directly or as a linking group (e.g. imino bond, ether bond, thioether bond, carbonamide bond, sulfonamide bond, ureido bond, ester bond, imide bond, carbamoyl bond, sulfamoyl bond, etc.). alone or in combination). Some specific examples of the ballast group are described below.

Alkyl groups and alkenyl groups (e.g. dodecyl group, octadecyl group), alkoxyalkyl groups (e.g. Japanese Patent Publication No. 3
3-(octyloxy)propyl group, 3-(2-ethylundecyloxy)propyl group), alkylaryl group (e.g., 4
-nonylphenyl group, 2,4-di-tert-butylphenyl group), alkylaryloxyalkyl group (e.g.
2,4-dimono-rt-bentylbutenoxymethyl group, Q
-(2,4-di-bentylphenoxy)propyl group, 1-(3-bentadecylphenoxy)-ethyl group, etc.), acylamidoalkyl group (e.g., U.S. Pat.
337,344 and 3,418,12, 2-(N-butylhexadecanamido)ethyl group, etc.), alkoxyaryl and aryloxyaryl groups (for example, 4-( n-octadecyloxy)phenyl group, 4-(4-n-dodecylphenyloxy)phenyl group, etc.), a long-chain aliphatic group of alkyl or alkenyl, and a water-solubilizing group such as carboxyl or sulfo group. (e.g., 1-carboxymethyl-2-nonanedecenyl group, 1-sulfoheptadecyl group, etc.), alkyl groups substituted with ester groups (e.g., 1-ethoxycarbonylheptadecyl group, 2-(n
-dodecyloxycarbonyl)ethyl group, etc.), an alkyl group substituted with an aryl group or a heterocyclic group (e.g., 2-[4-(3-methoxycarbonyluneicosanamido)phenyl]ethyl group, 2-[4 -(21n-octadecylsuccinimide)phenyl]ethyl group, etc.)
, and an aryl group substituted with an aryloxyalkoxycarbonyl group (for example, a 4-[4-(2,4-di-rt-bentylphenyloxy)-2-methylpropyloxycarbonyl]phenyl group, etc.). Particularly preferred among the above organic ballast groups are those bonded to a linking group as represented by the following general formula.

-CON daily R7 ○1 R9 (skin) -○1 R
I.

(W)-CONHR9
(K) Here, R7 represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as a propylene group or a butylene group, and R8 is hydrogen or a carbon number 1
preferably represents an alkyl group having 1 to 6 carbon atoms, for example, 91 amyl group, and n is an integer of 1 to 5 (
It preferably represents 1 or 2).

R9 represents an alkyl group having 4 to 30 carbon atoms, preferably 10 to 20 carbon atoms, such as a dodecyl group, a tetradecyl group, and a hexadecyl group. R1o is an alkyl group having 8 to 3 carbon atoms, preferably 10 to 20 carbon atoms (for example, hexadecyl group, octadecyl group, etc.) or a substituted alkyl group having 8 or more carbon atoms in total (the alkyl residue has 1 or more carbon atoms. As a substituent is, for example, a carbamoyl group.
Specific examples of the sulfamoyl group represented by formula (V) include the following.

Furthermore, “Research Disclosure”, 13
The groups described in Vol. 0, No. 13024 (1975 2 self-published) are also effective as Y.

Among the DRR compounds prepared using the compound of the present invention as an intermediate, preferred compounds are those represented by the above general formula (W), and the expressions in the formula are as follows: RI is a 1C ratio CH2- and: R2 is a straight chain or branched alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.); D- is of formula (0); and in formula (B), Q is a cyano group, M is a hydrogen atom; m is 0 or 1, and Y represents a sulfamoyl group represented by the general formula (V).

Particularly preferred DRR compounds are represented by the above-mentioned general formula (W), and the expressions in the formula are as shown below: RI is -CQC day 21; R2 has 1 to 1 carbon atoms; 4 is a linear unsubstituted alkyl; D1 is represented by the formula (D), and in the formula (0), Q is a cyano group and M is a hydrogen atom; m is 0; Y In addition to the ballast group, an alkyl group was bonded to the meta position relative to the hydroxyl group.

-Represents a hydroxyphenylsulfamoyl group. Specific examples of the DRR compound of general formula (W) are shown below.

Compound Y-1 (where R2=C is) Compound Y-2 A compound where R2=C2 in the formula of Compound Y-1 Compound Y-3 (R2=C ratio) Compound Y-4 Formula of Compound Y-3 In R2=C2day5 compound Compound Y-5 (However, R2=C is) Compound Y6 In the formula of compound Y-5 R2:C2day5 compound*
Compound Y-7 (however, R2=C ratio) Compound Y-8 In the formula of compound Y-7, the compound where R2=C2day5 Compound Y-9 (however, R2=C ratio) Compound Y-10 Formula of compound Y-9 In the formula of R2=C2day5 Compound Y-11 Compound Y-12 Compound Y-13 Compound Y-14 Compound Y-15 (where R2=CQ) Compound Y-16 In the formula of compound Y-15, R2=C2day5 Compound Y-17 Compound Y-18 Compound Y-19 Compound Y-20 Among the DRR compounds derived from the intermediate of the present invention, specific examples of D- in formula (N) are represented by formula (m) is shown below.

Compound M-1 (R2=C ratio) Compound M-2 In the formula of Compound M-1, R2=C25 Compound M-3 Compound M-4 (R3=H) Compound M-5 Compound M- In the formula of 4, R3=C The compound of compound M-6 In the formula of compound M-4, R3=n-C4 The compound of 9 Compound M-7 (However, R2=C&) Compound M-8 The formula of compound M-7 In the formula of R2=C2 day 5, the compound Compound M-9 (however R2=C ratio) Compound M-10 In the formula of compound M-9, R2=C2 day 5 compound H Compound M-11 Compound M-12 (however R2 =C4) Compound M-13 In the formula of Compound M-12, R2=C2 Day 5 Compound Compound M-14 Compound M-15 (However, R3=H) Compound M-16 In the formula of Compound M-15, R3=C In the formula of compound M-17 compound M-15, R3=C44-
Compound M-18 (however R2=C ratio) Compound M-19 In the formula of compound M-18 Compound M-20 Compound M-21 (however R3=H) In the formula of compound M-18 In the formula of Compound M-21, R3=C is the compound Compound M-23 In the formula of Compound M-21, R3=(n)
C4 day 9 compound Compound M-24 Compound M-25 In the formula of compound M-4 R3=C2 day 5-Compound M
-26 In the formula of compound M-4 R3 = C ratio Upon oxidation below, a novel magenta dye compound as shown in formula (X) or (M) is released.

These are included within the scope of the compounds of this invention. However, Q1, P, R1, and R2 have the same meanings as in formula (W).

The DRR compound is obtained by a condensation reaction between the intermediate of the present invention represented by the formula (Kari) (X is halogen) and the amine represented by the formula (Xm) or the formula (XW). However, Q, M. R1a and Rib and Rne and R2b are expressed by the formula (W
), and it is the same as the case of T and Gengawa mashiki (V).

X represents a halogen atom (for example, a chlorine atom or a fluorine atom. This condensation reaction is usually preferably carried out in the presence of a basic substance. Examples of such basic substances include:
Alkali or alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc.), aliphatic amines (e.g. triethylamine), aromatic amines (e.g. N,
N-jethylaniline, etc.), heteroaromatic amines such as (pyridine, quinoline, Q-,8- or y-picoline, lutidine, collidine, 4-(N,N-dimethylmino)pyridine, etc.), and heterocyclic bases (such as 1,5-diazapicyclo[4,3,0]nonene-5; 1,8-diazapicyclo[5,4,0]undecene-7, etc.). When × is chlorine, that is, when the formula (Kari) is sulfonyl chloride, the above-mentioned heteroaromatic amines (especially pyridine) are particularly excellent. Formula (Xm)
For example, the amine represented by
No. 4, No. 50-115528, No. 49-114424
No. 3,932,38, U.S. Patent No. 3,931,1
44, and "Research Disclosure" No. 13 Ikari, 13024 are representative.

As a typical method for synthesizing the amine represented by the formula (XN), in the route to synthesize the compound of the formula (J), the amine H
One strategy is to use a compound represented by formula (Xm) instead of NEIE2.

The compounds of the present invention are useful not only as intermediates for the DRR compounds described above, but also as monoazo dyes. A specific example of synthesizing the compound represented by formula (W) from the compound represented by formula (1) of the present invention will be described below for reference.

Reference Synthesis Example 1 Synthesis of Compound Y-1 N,N-dimethylacetamide 20', 4.0 g of 2-amino-4-hexadecyloxy 5-methyl-phenol hydrochloride group and 4 obtained in Synthesis Example 25 above ．． The base 3-cyano-4-[4-(2-methoxyethoxy)-5-chlorosulfonylphenylazo]-1-phenylphenyl-5-pyrazolone (compound B-1) was added.

4.7' of pyridine was added dropwise while stirring, and the mixture was left to stand at room temperature for 2 hours. After the reaction was completed, 30 parts of methanol and 10 parts of water were added to the reaction solution. After separating the precipitated crystals in a furnace, they were recrystallized using acetonitrile at 200 ml. Yield 5. Total m. p. 162-164qo Reference Synthesis Example 2 Synthesis of Compound Y-15'a) Synthesis of 2-[2-(2-methoxyethoxy)-5-nitrobenzenesulfonamide]-14-hexadecyloxy-5-methyl-phenol 20g 2-Amino-4-hexadecyloxy-5-methyl-phenol hydrochloride, 2-(2-methoxyethoxy)-5-nitrobenzenesulfonyl chloride obtained in the above Synthesis Example 9'a} of 1 base was mixed with 100% of tetrahydrofuran and pyridine. The mixture was added to a mixture of 10 and stirred at room temperature for 3 hours.

While stirring the reaction mixture, add 300 g of ice water and 50 g of concentrated hydrochloric acid.
Added to '. The precipitated crystals were collected and washed with water. After air drying, recrystallization was performed in 100% acetonitrile. Yield: 3 m. p. 85. Synthesis of 5-8 is 0'b'2-[2-(2-methoxyethoxy)-5-amino-benzenesulfonamide]-4-hexadecyloxy-5-methyl-phenol 3 male 2-[2 One (2
-methoxyethoxy)nitrobenzenesulfonamide] 14-hexadecyloxy5-methyl-phenol, 2 parts iron powder, 1 part iron tetroxide, 0. key ammonium chloride,
In addition to 300 ships of inpropyl alcohol along with water 25, reflux was performed for 1 hour in a steam tank.

After the reaction was completed, the mother liquor was filtered and cooled on ice, and the precipitated crystals were collected, washed with 50 ml of inpropyl alcohol, and then dried in a storm. Yield 2 total m. p. 142-144q0 'c) Synthesis of compound Y-15 Into 20 N,N-dimethylacetamide, the above 'b
5.9 g of 2-[2-methoxyethoxy)-5-amino-benzenesulfonamide]-14-hexadecyloxy-5-methyl-phenol obtained in Synthesis Example 25 and 3-cyano 4 obtained in Synthesis Example 25. 1 [41 (2-methoxyethoxy)
-5-chlorosulfonylphenylazo]-1-phenyl-5-pyrazolone4. Added the gunwale.

Add 1.6 parts of pyridine dropwise while stirring, and then add 2 parts of pyridine at room temperature.
I worshiped time. After the reaction is complete, add 30 parts of methanol and 1 part of water.
0 added me. The precipitated crystals were separated from the furnace and then recrystallized with 100% acetonitrile. Yield 8.7gm. p. 1~141℃ Reference Synthesis Example 3 Synthesis of Compound M-1 To 40' of N,N-dimethylacetamide, 2 female 2-
Amino-4-hexadecyloxy-5-methyl-phenol hydrochloride and 13 g of 2-(N-t) obtained in Synthesis Example 32 above
e-butylsulfamoyl)-4-[4-(2-methoxyethoxy)-5-chlorosulfonylphenylazo]
-5-methanesulfonamide-1-naphthol (compound B-4) was added.

While praying to the light, I dripped 10 drops of pyridine on it, and then worshiped it for two hours at room temperature. The reaction mixture was poured into 200 ml of ice water containing io hydrochloric acid, and the precipitated crystals were collected in a furnace and washed with water. After air drying, recrystallization was performed with 50% of methyl alcohol. Yield 5. female m. p. 140-1420 Reference Synthesis Example 4 Synthesis of Compound M-3 In Z of N,N-dimethylacetamide 20, 3.1 g of 2-amino-4-hexadecyloxy-5-methyl-phenol hydrochloride and the above synthesis example were obtained. 2-(1-pyrrolidinylsulfonyl)-41[4-(2-methoxyethoxy)-5-sulfochlorophenylazo]-5-methanesulfonamido-1-naphthol (Compound B-7)5. Added a female.

3.6' of pyridine was added dropwise while stirring, and then 2.6' of pyridine was added at room temperature.
I worshiped the time light. After the reaction, 30 parts methanol and 10 parts water
' was added to the reaction solution. The precipitated crystals were washed with 50 g of methanol after being boiled in a furnace. After air drying, recrystallization was performed with 50% of acetonitrile. Yield 4. female m. p. 105～
10 registers 0

Claims (1)

[Claims] 1. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R^1 is an alkylene group having 2 to 8 carbon atoms; R^2 is an alkyl group having 1 to 8 carbon atoms; E is - OH, ▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, E^1 and E^2 may be the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a 7-carbon number, respectively. ~15 aralkyl group or 6 to carbon atoms
represents 15 aryl groups. E^1 and E^2 may be linked directly or via an oxygen atom to form a 5- to 6-membered saturated heterocycle. ) or a halogen atom consisting of a chlorine atom, a bromine atom, and a fluorine atom; D represents a group represented by the following general formula (II) or (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, Q is a cyano group, a trifluoromethyl group, a carbamoyl group represented by -CONR^3R^4 (where R^3 represents a hydrogen atom or an alkyl group,
R^4 represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group. R^3 and R^4 may be connected directly or via an oxygen atom to form a ring; M is a hydrogen atom;
Alkyl group, sulfamoyl group represented by -SO_2NR^3R^4 (R^3, R^4 are the same as above)
, -COOR^5 (R^5 represents an alkyl group, phenyl group, or substituted phenyl group) or a halogen atom. ▲There are mathematical formulas, chemical formulas, tables, etc.▼However, Q^1 is a hydrogen atom, a halogen atom, -SO_2NR^3
Sulfamoyl group represented by R^4 (where R^3 and R^4 have the same meanings as in formula (II)), -SO
_2R^6 (R^6 represents an alkyl group or a benzyl group), a carboxyl group, -COOR^5 (R^5 has the same meaning as formula (II)), or -CONR^3R^4
(R^3, R^4 have the same meanings as in formula (II)); Q^2 is at the 5th or 8th position with respect to OH,
Hydroxyl group or -NH-COR^4 or -NHSO_2
R^4 (In the formula, R^4 is the same as the formula (I
(synonymous with case I)).