JP2692767B2 - Method for producing quinacridone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to a method for producing quinacridone.

(Prior Art) 6,13-Dihydroquinacridones are known as an intermediate raw material for quinacridone, which is a red pigment.

In U.S. Pat. No. 2,821,541, 2,5-di (allylanilino) -3,6-dihydroterephthalic acid dialkyl esters obtained by condensing succinyl succinic acid dialkyl ester and aromatic amines are referred to as "Dowtherm A". The method of producing 6,13-dihydroquinacridones by synthesizing a eutectic mixture sold under the trademark of Dow Chemical Co., Ltd. in an inert high-boiling-point solvent, and then heating and ring-closing. Have been described. However, this method is not only low in yield, but also requires condensation to be carried out under reduced pressure while dehydrating, which is extremely industrially disadvantageous.

As another method, a method of carrying out the condensation reaction in the absence of an inert high boiling point solvent is known. However, in this method, unreacted aromatic amines coexisting with 2,5-di (allylamino) -3,6-dihydroterephthalic acid dialkyl esters adversely affect the production of 6,13-diidroquinacridones, There is a problem that the unreacted aromatic amines should be removed as much as possible. of course,
Aromatic amines can be distilled off under reduced pressure.
Since the di (allylamino) -3,6-dihydroterephthalic acid dialkyl ester is obtained as a solid, it is necessary to perform complicated operations such as filtration and washing before the subsequent cyclization step. Moreover, even if such 2,5-di (allylamino) -3,6-dihydroterephthalic acid dialkyl ester is dissolved in an inert high boiling point solvent and heated at a high temperature for cyclization, a high yield of 6,5 is obtained. It is not possible to obtain 13-dihydroquinacridones. However, according to Japanese Patent Application Laid-Open No. 53-26823, 2,5-di (allylamino) -3,6-dihydroterephthalic acid dialkyl esters were synthesized in the absence of an inert high-boiling solvent to give aromatic compounds. The presence of an inert high-boiling-point solvent when distilling out the group amines under reduced pressure gives 2,5-di (allylamino) -3,6-dihydroterephthalic acid dialkyl esters as a solution or slurry. It is described that it is easy to handle, and the ring-closing reaction is carried out by supplying it to a pre-heated high-boiling point solvent as it is, to obtain 6,13-dihydroquinacridone of high purity in high yield. However, since the 2,5-di (allylamino) -3,6-dihydroterephthalic acid dialkyl ester used here basically does not wash aromatic amines, it adversely affects the production of 6,13-dihydroquinacridone. There is no difference in giving. Further examples of the inert high-boiling solvent used include "Dowtherm A" (Dow Chemical Co.), diphenylmethane, and 1,1-diphenylethane, which are solids in some cases with melting points close to room temperature. Therefore, it is not easy to handle.

According to JP-A-54-119532, tert-amylbenzene, tert-hexylbenzene, tert-heptylbenzene and the like are mentioned as the inert high-boiling solvent to be used,
Nitrogen pressure is increased to 20 atm and heated to a predetermined temperature,
Not industrially advantageous.

JP-B-55-47626 and US Pat. No. 28241541 disclose that methylnaphthalene, biphenyl, diphenyl oxide and the like are used, but since these have a lower boiling point than "Dowtherm A", the yield and the purity of the product are higher. Inferior to the product synthesized with "Dowtherm A". When the inert high-boiling solvent has a low boiling point, for example, according to JP-A-57-40562, 2,5-di (allylanilino) -3,6-
When the dialkyl esters are heated, undesired ring closure moieties are obtained.

Further, JP-A-57-57749 discloses a method for producing 6,13-dihydroquinacridones using dibenzyl ether, and JP-A-62-205163 discloses a dimethyl diphenyl ether isomer mixture. Although it is
None of them are satisfactory in yield, quality and reaction time.

(Problems to be Solved by the Invention) Industrially producing high-yield, high-purity 6,13-dihydroquinacridone in a short time from 2,5-di (allylamino) 3,6-terephthalic acid dialkyl esters An advantageous method is provided.

[Configuration of the invention]

(Means for Solving the Problems) The present invention essentially comprises 2,5- (diallylamino) -3,6-dihydroterephthalic acid dialkyl esters in a single substance or a mixture of naphthalene derivatives represented by the formula (I). A step of obtaining 6,13-dihydroquinacridone, which is characterized by heating to 250 ° C. to 330 ° C. in an atmosphere not containing oxygen, and a step of oxidizing the 6,13-dihydroquinacridone. Relates to a method for producing quinacridone.

(In the formula, R ₁ represents a C ₁ -C ₄ alkyl group, n is 1,
2, 3 and 4 (except C ₁ when n = 1). The naphthalene derivative (I) used in the present invention is preferably an ethylnaphthalene isomer mixture, a propylnaphthalene isomer mixture, a butylnaphthalene isomer mixture, a dimethylnaphthalene isomer mixture, a diethylnaphthalene isomer mixture, dipropyl. Naphthalene isomer mixture, dibutylnaphthalene isomer mixture, trimethylnaphthalene isomer mixture, triethylnaphthalene isomer mixture, tributylnaphthalene isomer mixture, tetramethylnaphthalene isomer mixture, tetraethylnaphthalene isomer mixture, tetrapropylnaphthalene isomer mixture,
There is a mixture of tetrabutylnaphthalene isomers. A mixture of the above-mentioned alkylnaphthalene isomer mixtures in an appropriate ratio may be used.

The 2,5-di (allylamino) -3,6-terephthalic acid dialkyl ester is represented by the following general formula (II).

(In the formula, R ₂ and R ₃ are lower alkyl groups such as methyl and ethyl, and X is hydrogen-substituted F, Cl, Br, I, —OH,
-NO _2, -CF _3, optionally substituted C ₁ -C ₄ alkyl group, optionally substituted C ₁ -C ₄ alkoxy, phenyl, cyclohexyl, _{phenoxy, -COOH, -COO-C 1 ~C} 4 alkyl, - S
O ₃ H, phenylamino, benzylamino, -N (C
_{H 3) 2, -SO 2 NH} 2, -SO 2 N (CH 3) 2, pyridyl, -CON
H ₂ or —CON (CH ₃ ) ₂ is shown (provided that at least one ortho position is hydrogen with respect to the —NH— group), and n is an integer of 0, 1, or 2. ) 2,5-Di (allylamino) -3,6-terephthalic acid dialkyl esters can be synthesized using the naphthalene derivative (I) as a solvent, but methanol is used in the absence of such an inert high-boiling solvent. Alternatively, using ethanol, toluene, xylene as a solvent, dialkyl succinyl succinate and an aromatic amine are condensed at a temperature of 60 to 120 ° C. using an acid such as hydrochloric acid, sulfuric acid or acetic acid as a catalyst, and the product is once filtered to be condensed. It is preferable to use a product obtained by thoroughly washing the aromatic amine with the solvent used.

The 2,5-di (allylamino) -3,6-dihydroterephthalic acid dialkyl ester may be in a paste state containing a condensation solvent after washing or in a dried state, and may have a dry weight of 5 to 20%.
Using the naphthalene derivative (I) in an amount of 1-fold by weight as a solvent, heating is carried out at 250 to 320 ° C. for 30 to 90 minutes in an atmosphere of an inert gas such as nitrogen, argon or carbon dioxide. Alternatively, 2,5-di (arlyamino) -3,6-dihydroterephthalic acid dialkyl ester and naphthalene derivative (I)
Preheat the mixture of 100 to 170 ° C. under an atmosphere of an inert gas and measure it in a naphthalene derivative (I) boiled at 250 to 320 ° C. under an atmosphere of an inert gas in 15 to 120 minutes,
The cyclization is completed by heating for 15 to 30 minutes under reflux and distilling off alkyl alcohol such as methanol and ethanol. After cyclization of the naphthalene derivative (I) in an inert high-boiling solvent, an appropriately substituted suspension of 6,13-dihydroquinacridones is obtained and treated in a conventional manner. For example, the product can be filtered off with suction at a temperature of 170 ° C. or lower, and the suction filter cake obtained can be washed with alcohol, preferably methanol to remove the adhering solvent and by-products, if necessary. Then it can then be extracted by stirring again in hot methanol to remove the residue of the inert high-boiling solvent of the naphthalene derivative (I). All wastes (mother liquor, washing liquor) obtained in the cyclization process are treated by distillation without any problems, and the naphthalene derivative (I)
The high boiling point solvent and methanol can be recovered in high yield, and the residue can be burned in liquid form.

The preparation of 6,13-dihydroquinacridones from the naphthalene derivatives (I) of 2,5-hr (allylanilino) -3,6-dihydroterephthalic acid dialkyl esters of the present invention in an inert high-boiling solvent is conventional. Since the deesterification reaction related to the ring closure reaction occurs very quickly as compared with the method used, it is possible to reduce the production of by-products infinitely, and furthermore, the reaction takes place very quickly. The time required for manufacturing can be shortened.

The naphthalene derivative (I) of the present invention includes alcohols,
In particular, since the solubility of methanol is lower than that of conventionally known "Dowtherm A", methylnaphthalene, diphenylmethane, 1,1-diphenylethane, etc., when alcohols are present in the solvent, they are easily distilled off at the boiling point temperature. The dissolved amount of alcohols produced by the deesterification reaction of 5,5-di (allylamino) -3,6-dihydroterephthalic acid dialkyl ester in the solvent is small, and the main reaction is not only completed quickly but also by-products Production can be reduced.

2,5-Di (allylamino) -3,6-by cyclization reaction of the naphthalene derivative (I) of the present invention in an inert high-boiling solvent.
The synthesis of appropriately substituted 6,13-dihydroquinacridones starting from dihydroterephthalic acid dialkyl esters proceeds in high yield.

The products synthesized according to the invention are obtained in a very pure form, as shown by IR and UV spectroscopy data.
They can further be processed containing methanol or in the form of an aqueous paste or in dry form.

The oxidation of 6,13-dihydroquinacridones is known in principle. (For example, US Patent No. 2821529, Examples 9 to 15, British Patent No. 909602, Examples 1 to 6, British Patent No. 911477, Examples 1 to 11, etc.) 6,13- manufactured by the present invention Dihydroquinacridones are, for example, m-nitrobenzene sulfonic acid sodium carbonate, nitrobenzene, nitronaphthalene, nitrobenzene sulfonic acid and nitrobenzene carboxylic acid, nitrophenol, oxygen or air solvent of methanol, ethanol, acetone or ethylene glycol or glycol ether and water. It can be converted to the corresponding quinacridone by oxidation in the presence of alkali in the mixture at elevated temperature, if necessary under pressure and, if necessary, in the presence of dispersants and reaction promoters. The oxidation is preferably carried out with air in the presence of a dispersant, preferably an anionic dispersant, for example the condensation product of aromatic sulfonic acid and formaldehyde.

According to the present invention, for example, the following quinacridone can be synthesized. Quinacridone, 2,9-dichloroquinacridone, 3,10-dichloroquinacridone, 4,11-dichloroquinacridone, 2,9-dimethylquinacridone, 3,10-dimethylquinacridone, 4,11-dimethylquinacridone, 2,9
-Dimethoxyquinacridone, 2,9-diethoxyquinacridone, 2,4,9,11-tetrachloroquinacridone, 2,9-dicyclohexylquinacridone, 2,9-diphenylquinacridone, 3,10-dinitroquinacridone, 1,2,8 , 9-Tetrachloroquinacridone, 2,9-difluoroquinacridone and 2,9-dibromoquinacridone.

The present invention is further in the production of unsubstituted γ-type linear transquinacridone, especially β-type crystals of 6,13-dihydroquinacridone obtained by carrying out the cyclization reaction at a temperature of 300 ° C. or higher under normal pressure or pressure. I knew it was. Therefore, in order to synthesize γ-type quinacridone as described in U.S. Pat.No. 3352867, a general method is performed after transferring α-type 6,13-dihydroquinacridone to β-type 6,13-dihydroquinacridone. It can be obtained by oxidization with, but since β-type 6,13-dihydroquinacridone can be obtained by the present invention, it was found that it can be obtained only by an oxidation reaction without a transfer step, and that the time required for the production can be significantly shortened. . Further, α-type 6,13-obtained by the present invention
The conversion of dihydroquinacridone to β-type 6,13-dihydroquinacridone is generally treated with a substantially anhydrous mixture of C1-C4 alcohol and alkali.

The unsubstituted γ-type linear transquinacridone obtained by the method of the present invention is characterized by high purity, high hiding power, high gloss and other remarkable coloring properties.

The method according to the invention is explained in more detail by the following examples.

Hereinafter, the present invention will be described with reference to examples. In the examples, “parts” means “parts by weight” and “%” means “% by weight”.

Example 1 To 30 parts of well-dried 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester, 150 parts of dimethylnaphthalene isomer mixture was placed in a flask having an outlet valve at the bottom of 200 ml under a nitrogen gas atmosphere. While stirring with 120-1
Heat to 70 ° C. This hot mixture was then stirred in a 500 ml flask under a nitrogen gas atmosphere with stirring in 150 parts of the above dimethylnaphthalene isomer mixture boiling at 258 ° C.
Weigh out over 0-40 minutes, then mix at 258-262 ° C
Hold at (reflux) for another 30 minutes.

1 in a mixture of dimethylnaphthalene isomers boiled at 258 ° C
From the moment when the mixture of 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester and dimethylnaphthalene isomers at 20 to 170 ℃ was measured, with the evolution of methanol, 6,13
-The formation reaction of dihydroquinacridone starts, and the generation of methanol almost disappears immediately after the start of the reflux at 258 ° C.

After cooling to 100 ° C, the nitrogen gas atmosphere was released, the contents were filtered, washed with 500 ml of hot methanol, dried and α type 6,13
Obtained 24.47 parts of dihydroquinacridone (98.10% of theory). The purity was 98% or more according to IR and UV spectra.

Comparative Example 1. To 30 parts of well-dried 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester, 150 parts of a methylnaphthalene isomer mixture was added with 200 ml of nitrogen gas in the same reaction vessel as in Example 1. Heat to 120 ° C to 170 ° C with stirring under atmosphere. This hot mixture is then weighed into 150 parts of the above-mentioned methylnaphthalene isomer mixture boiling at 244 ° C. under stirring in a 500 ml flask under a nitrogen gas atmosphere over 20-40 minutes, followed by the mixture. To 241-244 ° C (reflux)
Hold for 30 minutes.

1 in a mixture of dimethylnaphthalene isomers boiled at 244 ° C
From the moment when a mixture of 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester and dimethylnaphthalene isomers at 20 to 170 ° C was metered in, methanol was generated from the moment it was measured.
-The formation reaction of dihydroquinacridone starts and the generation of methanol almost disappears immediately after the start of reflux at 244 ° C.

After cooling to 100 ° C, the nitrogen gas atmosphere was released, the contents were filtered, washed with 500 ml of hot methanol, dried and α type 6,13
20.21 parts of dihydroquinacridone (81.10% of theory) are obtained. The purity was 96% according to IR and UV spectra.

Comparative Example 2. A similar experiment was conducted using “Dowtherm A” in place of the methylnaphthalene used in Comparative Example 1. as a result,
α-type 6,13-dihydroquinacridone 23.85 parts (theoretical amount of 95.
70%).

Example 2. 2,5-Dianilino-3,6-dihydroterephthalic acid dimethyl ester used in Example 1 was replaced by 2,5-di (p-chloroanilino) -3,6-dihydroterephthalic acid dimethyl ester. A similar reaction was carried out using 30 parts.
As a result, 2,9-dichloro-6,13-dihydroquinacridone 2
4.68 parts (96.01% of theory) were obtained.

Comparative Example 3. 2,5-Di (p-chloroanilino) -3,6-dihydroterephthalic acid dimethyl ester was used in place of 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester used in Example 1. Using 30 parts, the same reaction was carried out using the methylnaphthalene isomer mixture instead of the dimethylnaphthalene isomer mixture. As a result, 2,9-dichloro-
6,13-Dihydroquinacridone 19.63 parts (theoretical amount of 76.37
%).

Example 3. Instead of 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester used in Example 1, 2,5-di (m-chloroanilino) -3,6-dihydroterephthalic acid dimethyl ester was used. A similar reaction was carried out using 30 parts.
As a result, 3,10-dichloro-6,13-dihydroquinacridone
24.45 parts (95.12% of the logic) were obtained.

Example 4. Instead of 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester used in Example 1, 2,5-di (p-toluidino) -3,6-dihydroterephthalic acid dimethyl ester was used. A similar reaction was carried out using 30 parts. As a result, 2,9-dimethyl-6.13-dihydroquinacridone 24.
44 parts (96.71% of theory) were obtained.

Comparative Example of Example 4. In place of the 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester used in Example 1, 2,5-di (p-toluidino) -3,6-dihydroterephthalate was used. A similar reaction was carried out using 30 parts of acid dimethyl ester and the methylnaphthalene isomer mixture instead of the dimethylnaphthalene isomer mixture. As a result, 2,9-dimethyl-6,13
Obtained 19.78 parts of dihydroquinacridone (78.27% of theory).

Examples 5-13. Instead of the 2,5-dianilino-3,6-dihydroterephthalic acid dimethyl ester used in Example 1, 2,5-di (allylanilino) -3, shown in the table below, The same reaction was carried out using 30 parts of 6-dihydroterephthalic acid dialkyl esters, and the results are shown.

Example 14. A similar reaction was carried out using an ethylnaphthalene isomer mixture instead of the dimethylnaphthalene isomer mixture used in Example 1. The boiling point temperature was 259 ° C. As a result, 24.08 parts of 6,13-dihydroquinacridone (theoretical amount of 9
6.43%) was obtained.

Example 15. The same reaction as in Example 1 was carried out in a pressure reaction vessel at a reaction temperature (reflux temperature) of 310 ° C., resulting in β-type 6,13.
Obtained 24.32 parts of dihydroquinacridone (97.59% of theory).

Examples 16 to 19. The results of carrying out the same reaction using the compounds shown in the following table instead of the dimethylnaphthalene isomer mixture used in Example 1 are shown.

Example 20. A similar reaction was carried out using an inert high-boiling point solvent in which the naphthalene derivative was mixed in the following mixing ratio in place of the dimethylnaphthalene isomer mixture used in Example 1.
The boiling point temperature was 263 ° C. As a result, 24.20 parts of 6,13-dihydroquinacridone (97.11% of theory) were obtained.

Naphthalene derivative name Weight ratio (parts) Ethylnaphthalene isomer 25.65 Dimethylnaphthalene isomer 270.30 Diethylnaphthalene isomer 4.05 Example 21. The dimethylnaphthalene isomer mixture used in Example 1 was replaced with the following naphthalene. A similar reaction was carried out using an inert high boiling point solvent mixed with the derivative.
As a result, 23.86 parts of 6,13-dihydroquinacridone (95.74% of theory) were obtained.

Naphthalene derivative name Weight ratio (parts) Ethylnaphthalene isomer 4.59 Dimethylnaphthalene isomer 76.80 Dimethylnaphthalene isomer 211.50 Trimethylnaphthalene isomer 7.11 Example 22. In a stainless steel flask, 79 parts of methanol and 12 parts of 50% NaOH aqueous solution were well stirred. Then, 10 parts of 6,13-dihydroquinacridone prepared in Example 1 and 10 parts of sodium m-nitrobenzenesulfonate were gradually mixed and refluxed at 70 to 75 ° C for 3 to 5 hours. The mixture is cooled to 40 ° C. or lower and then filtered, and the cake is washed with hot water and dried until the distillate becomes colorless and transparent. As a result the unsubstituted linear transformer quinacridone
We obtained 9.78 parts (98.4% of theory). As a result of determining the purity by IR and UV spectra, 98.5% quinacridone and 1.2%
6,13-Dihydroquinacridone could be detected.

Example 23. β-type 6,13-dihydroquinacridone 10 obtained in Example 15.
Part was subjected to an oxidation reaction in the same manner as in Example 22. As a result, 9.72 parts of unsubstituted γ-type linear transquinacridone (theoretical amount of 9
7.82%).

Example 24. The α-type 6,13-dihydroquinacridone of Example 22 was replaced with 10 parts of 2,9-dichloro-6,13-dihydroquinacridone obtained in Example 2 and the same reaction was carried out. However, the reaction was carried out in a reaction pressure pressurization reactor, and the reaction temperature was 100 ° C. As a result, 9.68 parts of 2,9-dichloroquinacridone (the theoretical amount of 97.3
%).

Example 25. 10 parts of 2,9-dimethyl-6,13-dihydroquinacridone obtained in Example 4 was replaced with 2,9-dichloro-6,13-dihydroquinacridone of Example 10. As a result,
2,9-Dimethylquinacridone 9.53 parts (95.9% of theory)
I got

(Effects of the Invention) Cyclization of 2,5-di (allylanilino) -3,6-dihydroterephthalic acid dialkyl esters to 6,13-dihydroquinacridones using an inert high-boiling solvent of the naphthalene derivative of the present invention. Since the deesterification reaction involved in the cyclization proceeds very rapidly and the formation of by-products can be sufficiently prevented, the reaction was appropriately substituted with high purity and high purity in a short time. -Dihydroquinacridones are obtained. Further, by oxidizing the 6,13-dihydroquinacridones obtained by the present invention by a known method, they are appropriately substituted with high yield, high purity, high hiding power, high gloss and other remarkable colorability. You can obtain the corresponding cinacridones. Further, in the production of the unsubstituted γ-type linear transquinacridone, it can be obtained by appropriately selecting an inert high-boiling point solvent of the naphthalene derivative and keeping the reaction temperature at 300 ° C. or higher under normal pressure or if necessary, under pressure. Since 13-dihydroquinacridone has a β-type crystal, it is possible to obtain an unsubstituted γ-type linear transquinacridone by oxidation without further crystal transition.

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Claims (1)

(57) [Claims] 1. A 2,5- (diallylamino) -3,6-dihydroterephthalic acid dialkyl ester in a naphthalene derivative represented by the formula (I) alone or in a mixture containing essentially no oxygen. Heat to 250 ℃ ~ 330 ℃ at 6,
A process for producing quinacridone, which comprises a step of obtaining 13-dihydroquinacridone and a step of oxidizing the 6,13-dihydroquinacridone. (In the formula, R ₁ represents a C ₁ -C ₄ alkyl group, n is 1,
2, 3 and 4 (except C ₁ when n = 1). )