JPS6046143B2 - Azo dye manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for synthesizing an azo dye having a quinone residue in the molecule from an amine having a hydroquinone residue in the molecule or a salt thereof.

Azo dyes with quinone residues in their molecules are useful compounds as dye intermediates and materials for color photosensitive materials. However, the synthesis of this compound is difficult and US Pat.
No. 22169 and No. 3307947 disclose other synthetic methods. The methods described in these patents first diazotize an amine with a hydroquinone residue protected by an acetyl group, perform azo coupling, and then remove the protecting group to obtain an azo dye with a hydroquinone residue. It is oxidized to synthesize an azo dye having a quinone residue. This method requires the extra step of first acetylating the hydroxyl group of hydroquinone, which is easily oxidized.

Furthermore, in the step of hydrolyzing to regenerate the hydroquinone moiety, since hydroquinone is particularly alkaline and unstable, the reaction must be carried out extremely carefully, which not only makes process control difficult but also results in poor yields. The object of the present invention is to provide a method for obtaining an azo dye having a quinone residue in two consecutive steps from an amine (including its salt) having a hydroquinone residue in the molecule as described in the above-mentioned known method. be.

That is, the present invention diazotizes an aromatic primary amine (including the corresponding ammonium salt) having a hydroquinone residue in its molecule with nitrous acid, and oxidizes the hydroquinone moiety to form a diazo compound having a quinone residue. to obtain,
By reacting this with a compound (generally called a coupler) that couples with a diazonium salt, they succeeded for the first time in obtaining an azo dye containing a quinone residue in good yield. The aromatic primary amines or the corresponding ammonium salts include, for example, U.S. Pat.
reen) JeChem, Eng, Data9, 232
(1964) and others, but are not limited thereto. The present invention is significant in performing oxidation to quinone simultaneously or sequentially with diazotization, and the bond between the hydroquinone residue and the aromatic primary amine is an essential part of the present invention. It can't be.

That is, any divalent group that is difficult to react with nitrous acid or an oxidizing agent may be present therebetween, and a hydroquinone residue may be directly bonded to the aromatic ring of the aromatic primary amine. As a bonding moiety, -CH2-, -CH2CH2-, -(C
H2) 3- is particularly advantageous because the raw materials are easily available. In the case of a secondary amide of carboxylic acid or a linking group containing -S-, the yield is low due to reaction with nitrous acid. One part of this amine is made into an acidic aqueous solution, diazotized by adding one part or more of an aqueous solution of nitrite, and then a solution of an oxidizing agent in an amount necessary for oxidizing the hydroquinone moiety is added to obtain a solution of the diazonium salt.

During this time, the reaction time is maintained at 15°C or lower, preferably 3°C or lower. The order of addition may be reversed or simultaneous to the above. There has never been an example of simultaneous diazotization and oxidation of hydroquinone to quinone using nitrous acid (usually liberated from nitrite with a strong acid) and an oxidizing agent. do not have. In addition to nitrous acid itself, oxidizing agents used in combination include those known as oxidizing agents for hydroquinone, such as those listed in Experimental Chemistry Course Volume 17 (Part 1) (Maruzen, 1957). compounds such as halogen acids such as chloric acid, bromate acid, iodic acid, perhalogen acids such as peroxyacids, hypohalous acids such as hypochlorous acid, nitric acid, bromic acid, chromic acid, permanganic acid , ferric chloride, etc. When the oxidizing agent is an acid, it is usually generated by a reaction between a corresponding metal salt, ammonium salt, etc., and a strong acid. Among these, nitrous acid and nitric acid are particularly preferred. In particular, when nitrous acid is used, diazotization and oxidation of the hydroquinone moiety can be performed with the same reactant, which is extremely advantageous in terms of reducing the number of steps and simplifying the operation. In this case, a total of 3 equivalents of nitrous acid is required, including 1 equivalent for diazotization and 2 equivalents for oxidation, based on the amine. However, a large excess is not desirable. Also, when an oxidizing agent other than nitrous acid is used, two equivalents of the oxidizing agent are required. Needless to say, excessive amounts are not desirable at this time. An unsubstituted quinone nucleus and a diazonium ion react intermolecularly.
Since this is already known (G.A. ReyrK)
1ds and J. A. VanA] 1an. ．． 0r'G.
Synth. COll. Vol. 4Nl5), it is difficult to predict the existence of a molecular species containing both a quinone nucleus and a diazonium nucleus in the same molecule, and the present invention provides new knowledge in this respect.

It is known to use nitrous acid simply as an oxidizing agent (L.F.F.
ieserJ. Amer. Chem. SOc. , 701
3165 (1931)) and diazotization is also a well-known reaction, but the present invention is the first example of simultaneous diazotization and oxidation using nitrous acid. Diazonium salts cannot be isolated as is customary for diazo compounds. However, the expected structure is demonstrated by reacting with various pullers in the subsequent coupling step to form the corresponding azo dyes. The coupling is carried out according to a conventional method, that is, by reacting the coupler with an organic solvent solution or aqueous solution and a diazonium salt aqueous solution at a temperature of 15° C. or lower. This is described in many books, such as Hiroshi Horiguchi's ``Synthetic Dyes'', Sankyo Publishing, 1968, Chapter 5. Couplers are organic compounds that undergo conventional diazo coupling, such as α- and β-naphthols, pyrazolones, phenols, anilines, α- and β-
-aminonaphthalene, β-dicarbonyl compounds, active methylene compounds, and derivatives thereof. The diazonium salt obtained by the present invention is extremely useful as an intermediate for many compounds including azo dyes.

Furthermore, azo dyes can be used as dyes themselves or as dye intermediates. Furthermore, the azo dyes listed below are particularly excellent in applications as described in US Pat. No. 3,307,943 as a type of dye for color photography. Five specific examples of azo dyes obtained by the present invention are shown below.

The present invention will be explained in more detail with reference to Examples below.

Example 1 Synthesis of Compound (1) 13.3q (0.05 mol) of 4-(2″·5″-dividroxyphenethyl)aniline hydrochloride was dissolved in 2.5% hydrochloric acid 60
After cooling to below O'C in a salt ice bath, nitrous acid. Aqueous solution 1 of sodium 11.0y (0.16 mol)
Two drops of 50ml were added.

After stirring for 1 to 2 hours, 1.0 y of sulfamic acid
was added to decompose excess nitrous acid, and then 45y of sodium acetate was added.

During these operations, crushed ice was added as needed to maintain the reaction temperature at 3°C.
I kept it below. The resulting diazonium salt solution was diluted with 4-isopropyloxy-1-naphthol at 10.1 V (0.05
It was added dropwise to 500 mt of an ethanol solution of mol) while keeping the temperature below 10°C. Next, 400 mt of saturated deuterated water was added dropwise, and 1. Stir for hours. After drying the precipitated crystals with a filter and then recrystallizing them from a mixed solvent of benzene and methanol, compound (1) with a melting point of 168-170°C was converted into 1
Obtained 1.2y. Elemental analysis value (%) actual value C73.62,
H5.37, N6.34 Calculated value C73.62, H5.4
λN6.36 Example 2 Compound by combined use of nitrous acid and nitric acid (
Synthesis of 1) 4-(2″·5″-dihydroxyphenethyl)aniline hydrochloride 3.0q (0.011 mol), 35%
0.2 ml of 2-ethylhexanol was added as an antifoaming agent to a solution consisting of 9 ml of hydrochloric acid and 150 ml of water, and the mixture was cooled to below 0-C in a salt ice bath.

An aqueous solution of 2.6y (0.038 mol) of sodium nitrite was added dropwise to this solution. After stirring was continued for 5 minutes at a temperature below 3°C, dilute nitric acid consisting of 3 mL of nitric acid (Dl. 38) and 20 ml of water was added dropwise.

After stirring the two powders, 1.0 y of sulfamic acid and then 20 y of sodium acetate were added.

The solution of the diazonium salt thus obtained was mixed with 4-isopropoxy-1-naphthol 2.0% in the same manner as in the example.
y (0.010 mol) to convert compound (1) into 2
．． I got 6y. Compound (1) thus obtained was identified by comparison with that obtained in Examples by thin layer chromatography, infrared absorption spectrum, ultraviolet absorption spectrum, and nuclear magnetic resonance spectrum. By using nitric acid in combination, the yield of compound (1) was improved and the by-product of hydroquinone was suppressed. This hydroquinone preparation (melting point 22
C) of 2-224 can be obtained by reduction of compound (1). Example 8 Synthesis of compound (1) by using nitrite and nitric acid in combination The dropping of the sodium nitrite solution and dilute nitric acid in Example 2 was reversed.

3.0 f (0.011 mol) of 4-(2''.5''-dihydroxyphenethyl)aniline hydrochloride is dissolved in 200 ml of water, and 30 ml of nitric acid (Dl. 38) is added at 3°C or below.

After stirring the two powders, add 0.8y of sodium nitrite to this solution.
A solution consisting of (0.011 mol) and 30 ml of water was added dropwise. After stirring for 4 times at 3° C. or below, 50 y of sodium acetate was added. The resulting diazonium salt was converted into 4-isopropyloxy-1-naphthol 2 in the same manner as in Example 1.
．． 0y(a). 01 mol) to form compound (1)
We get 2.8. This product was confirmed to be the same as the sample obtained in Example 1 by thin layer chromatography and various spectral data. Example 4 Synthesis of compound (1) using nitrous acid and chloric acid 4-(2
″・5″-dihydroxyphenethyl)aniline hydrochloride 3
．． A solution of 0.8y (0.011 mol) of sodium nitrite dissolved in 30 ml of water was added dropwise to a mixed solution of 0.0y (0.011 mol), 12 ml of 35% hydrochloric acid, and 150 ml of ice water at 0°C or lower.

After one powder, 30 mt of an aqueous solution of 1.0 y (0.0065 mol) of sodium chlorate was added dropwise at 2° C. or below, and stirring was continued for 2 min.

After adding 15 da of sodium acetate, 2.0 y of 4-isopropyloxy-1-naphthol (
0.01 mol) to obtain compound (1). This product was identified as the standard sample obtained in Example 1. Example 5 Synthesis of compound (1) by combined use of nitrous acid and roic acid 4-
To 150 mt of an aqueous solution of 3.0 y (0.011 mol) of (2"●5"-dihydroxyphenethyl)aniline hydrochloride was added 7 ml of concentrated sulfuric acid, and 0.8 g (a) of sodium nitrite was added.
Then, 30 mt of an aqueous solution of 2.3 f (0.01 mol) of ammonium persulfate was added dropwise.

During this time, the reaction temperature was kept below 1°C. After 1 powder, add 2.3 ammonium persulfate, 2.5 ml of concentrated sulfuric acid, and 3 ml of water.
A solution consisting of 0 ml was added dropwise.

After stirring the mixture, 40 y of sodium acetate was added.

The diazonium salt obtained in this way was prepared using 4-isopropoxy-1-naphthol 1.5y(a) in the same manner as in Example 1.
．． 0074 mol) to give compound (1) (yield: 0.0074 mol).
6y). Example 6 Synthesis of Compound 2 In the same manner as in Example 1, 4-(β-ethoxyethoxy)
-1-naphthol 11.6y melting point 148-149℃
12.8y of compound (2) was obtained.

Elemental analysis value (%) Actual value C7l. 48? SH5.4 Den N
6. l2 calculated value C7l. 47, H5.57, N5.95
Example 7 Synthesis of Compound (3) From 3.0 y of 4-(2″·5″-dihydroxyphenethyl)aniline hydrochloride to a diazo solution prepared in the same manner as in Example 1, ω-cyano 2-acetylbenzofuran 1 was added.
．． 9y1 Ethanol 200ml 11 Sodium hydroxide 0.
A solution consisting of 6y and 10 ml of water was added dropwise.

The resulting crystals were air-dried separately and then recrystallized from acetone to obtain 1.49% of compound (3) with a melting point of 175-177°C.
b Elemental analysis value (%) Actual value C7O. to 9H3.9λNlO. 2l calculated value C7O. 9l, H4. O\N9.93 Example 8 Synthesis of compound (4) 1. In the same manner as in Example 7, from 2.8q of N-hexyl-1-phenyl-5-pyrazolone-3-carboxamide, a compound with a melting point of 1
0.2 g of compound (4) at 21-124°C was obtained.

Elemental analysis value (%) 1Actual value C68.6gsH5.9SakNl3.48Calculated value C68
．． 57, H5.9 to Nl3.33 Example 9 Compound (5)
Synthesis of 4-(2″●5″-dihydroxyphenethyl)A diazo solution prepared in the same manner as in Example 1 from 3.0q of aniline hydrochloride was mixed with 1.3y of m-methoxyphenol, 10y of sodium bicarbonate, and engineered ethanol. It was added dropwise to a suspension consisting of 150ml.

The resulting crystals were air-dried and then recrystallized from ethanol.
2.7y of compound (5) having a melting point of 2183-186°C was obtained. Elemental analysis value (%) Actual value C69.5ゥH4.9λN
7.7O calculated value C69.6O, H5. OO,. N7.7
3 Example 10 Synthesis of compound (13) (a) Synthesis of 2,5-dimethoxy-3''-nitrobenzophenone Dissolve m-nitrobenzoyl chloride 372y...p-dimethoxybenzene 280f in methylene chloride 1.6e and stir. 300y of aluminum chloride was added to the bottom.

After standing overnight, it was poured into ice water and the organic layer was separated. After distilling off the methylene chloride, the residue was recrystallized from ethanol to obtain the title compound 470y (melting point: 98°C) as pale yellow crystals. (b) 2,5-dimethoxy 3″-
Synthesis of aminobenzhydrol 100y of 2●5-dimethoxy3''-nitrobenzophenone obtained in (a) was dissolved in 1.3e of ethanol, and after adding 10% palladium on carbon catalyst, using an autoclave, the initial pressure of hydrogen was 100k.
gIcIt11 Hydrogenation was carried out at 30°C for 8 hours.

After the catalyst was removed, the P solution was concentrated to precipitate white crystals. The title compound 57y was obtained by air drying.
Melting point 132-134°C.・)1,4-dimethoxy2-
Synthesis of (3″-aminobenzyl)benzene Acetic acid 300m
After adding 96 y of zinc powder and 50 y of 2●5-dimethoxy-3''-aminobenzhydrol synthesized in (b), 240 ml of 35% hydrochloric acid was added dropwise at 80°C.

After 3 times, 2407n1 of 35% hydrochloric acid was added dropwise.

After stirring for 2 hours, the mixture was cooled, the supernatant liquid was taken, and the mixture was neutralized to pH5 with an aqueous sodium hydroxide solution. The precipitated oil was extracted with ethyl acetate and washed with hydrogenated sodium chloride solution. It was dried over anhydrous sodium sulfate and distilled under reduced pressure on an oil bath. Collect the fraction with a boiling point of 170 to 175 lC/1TrrmHg,
crystallized. The melting point was 81-84°C, and the yield was 36y. d) Synthesis of 3-hydroquinonylmethylaniline (c
) 1,4-dimethoxy-2-(3″-aminobenzyl)benzene 27y synthesized in 46% hydrobromic acid was mixed and refluxed on an oil bath for 1 to 2 hours.Crystals will precipitate when cooled with ice. Take it cold and add it to 200 ml of water.
mt and neutralized by adding 25 g of sodium acetate.
? The separated free amine was recrystallized from ethanol benzene (1:3 volume ratio) to obtain 16 g of the title compound. Melting point 1
51-157C0e) Synthesis of Compound (13) 8.4y of 3-hydroquinonylmethylaniline synthesized in (d), 400Tnt of ice water, 27ml of concentrated hydrochloric acid and 0.6mt of octyl alcohol were mixed and cooled to 0°C.

While stirring at a temperature below 2°C, 100 ml of an aqueous solution of 8.4 q of sodium nitrite was added dropwise in one drop.

After stirring for 9 minutes at 2°C or less, 1.0y of sulfamic acid was added.
Then 47y of sodium acetate was added.

400 ml of an ethanol solution containing 7.5 g of thioindoxy-2-carboxylic acid and an aqueous solution of sodium hydroxide (NaO
H2. A mixture of Oy and 10 ml of water was poured into the above diazo solution at 15°C or lower. The precipitated crystals were taken out by suction and air-dried. 1,2-dichloroethane-ethyl acetate (
Recrystallized from 1:1 volume ratio), melting point 189-190'
The title compound 9.4y of C was obtained as orange crystals.

Elemental analysis value (%) Actual value C67.3sH3. F! ? SN7.7; Calculated value (
C2lHl4N2O3S):C67.4SH3. F3s
N7.5 Example 11 Synthesis of compound (14) From 3-hydroquinonylmethylaniline 10.0 Da,
The 3-quinonylmethylphenyldiazonium salt solution obtained in the same manner as Example 10 (e) was coupled with 7.8y of 2-(2″-cyanoacetyl)coumarone to obtain 7.0g of compound (14). Obtained.

Melting point: 196-197°C. Elemental analysis value (%) Actual value C7O. 5. H3. F3sNlO. l calculated value (C
24Hl5N3O4):C7O. Tun H3.

7.NlO. 3 Example 12 Synthesis of compound (19) (a) 2●Synthesis of 5-dimethoxy 3″-nitro 4″-methylbenzophenone 3-nitro 4-methylbenzoyl chloride 96.0y and p-dimethoxybenzene 6
8.0y was subjected to Friedel-Crafts reaction in the same manner as in Example 10(a) to obtain the title compound 65.0y as pale yellow crystals.

Melting point: 109-110°C (recrystallized from ethyl acetate). (
b) Synthesis of 2,5-dimethoxy-3''-amino-4''-methylbenzhydrol The compound obtained in (a) was mixed with 50.
After dissolving 0y in ethanol 1.3e and adding Raney nickel catalyst 1f, hydrogenation was carried out using an autoclave at an initial hydrogen pressure of 85 kgId80°C for 7 hours.

After removing the catalyst, the liquid was concentrated to give white crystals. After air drying, the title compound 40.5 was obtained. Melting point 112-113°C. (c) 1◆4-dimethoxy2-(
Compound 33.0f obtained in synthesis (b) of 3″-amino-41-methylbenzyl)benzene was synthesized in Example 10 (c
) to obtain the title compound 21.0y.

Boiling point 168-170°C/1W$LHgO melting point 64°C. (
d) Synthesis of 5-hydroquinonylmethyl-2-methyl-aniline From 21.0 g of the compound obtained in (c), 15.0 g of the title compound was obtained by the same treatment as in Example 10 (d).
I got y.

Recrystallization from ethyl acetate-benzene (1:2 volume ratio) gave a melting point of 152-153'C. (e) Compound (1
Synthesis of 9) 5-hydroquinonylmethyl-2-methylaniline synthesized in (b) 5.0y1 ice water 200mt1
19 ml of concentrated hydrochloric acid and 0.5 ml of octyl alcohol were mixed and cooled to 0°C.

While stirring, add 40ml of an aqueous solution of 5.2y of sodium nitrite.
L was added dropwise. After stirring the mixture at a temperature below 2% C, 19f of sodium acetate was added.

400 TLL of ethanol solution of 3.7y of 2-(2″-cyanoacetyl)coumaron and aqueous sodium hydroxide solution (N
aOHl. ly and 20 mt of water) was added to the above diazo solution at 15°C or lower.

The precipitated crystals were collected by suction, air-dried, and then recrystallized from 1,2-chloroethane to obtain a compound (19
) 5.7y was obtained as yellow crystals. Elemental analysis value (%) Actual value C7O. 7, H4. to N9.6; Calculated value (C25Hl7N3O4): C7O. 9. H4.
1, N9.9 Example 13 Synthesis of compound (21) 5-hydroquinonylmethyl-2-hydroxyaniline 19.2y1 Ice water 1e1 Concentrated hydrochloric acid 60mt and octyl alcohol 3ml were mixed and dissolved and cooled to 0°C.

An aqueous solution of 17.5 fI of sodium nitrite with stirring 10
0ml was added dropwise at 0°C. After stirring at 2° C. or below for 8 minutes, 1.0 q of sulfamic acid and 100 y of sodium acetate were added.

An ethanol solution of 15.0 y of 2-(2″-cyanoacetyl)coumaron and an aqueous solution of 4.0 y of sodium hydroxide (
20 ml) was mixed and poured into the above diazo solution.

The precipitated crystals were filtered and recrystallized from 1,2-dichloroethane to obtain the title compound 17. with a melting point of 204-205°C.
2q was obtained as orange crystals. Elemental analysis value (%) Actual value C68. O, H3.4, N9.6; Calculated value (C2
4Hl5N3O5)C67.8. H3. Den N9.9 Example 14 Synthesis of Compound (22) In the same manner as in Example 13, a diazo solution was prepared from 4.6y of 5-hydroquinonylmethyl-2-hydroxyaniline, and 2-(2″-cyanoacetyl )-3-Methylcoumarone 4.0y to give the title compound 2.8y
I got it.

Melting point: 205-208°C (recrystallized from ethyl acetate). Elemental analysis value (%) Actual value C68. To H3.9. N9.6 Calculated value (C25Hl7N3O5) C68. λH3. Question N9.6

Claims (1)

[Claims] 1. A diazonium salt having a quinone residue in the molecule is obtained by reacting an aromatic primary amine having a hydroquinone residue in the molecule with a combination of nitrous acid and an oxidizing agent, and reacting this with a coupler. A manufacturing method for azo dyes that have quinone residues in their molecules.