JPS595148B2 - Shinkinai Soindoline Yudou Taigan Ryouno Seihou - Google Patents

Description

Detailed Description of the Invention The present invention provides novel symmetric or asymmetric isoindoline derivatives represented by the general formula 300H0 11N11 /C\/\C\B, c/c′′ψ(O/゛3511(( Concerning the manufacturing method of pigments.

In the above general formula, A is O-phenylene group or 2.3
-naphthalene group, B means a group selected from O-phenylene group, 2,3-naphthalene group or 1,8-naphthalene group which may be substituted with up to 4 halogen atoms. The present inventors conducted research on pigments containing indandione compounds, which are known in the literature but only partially used for medicinal purposes, and found that the compounds and isoindolenine derivatives are related to each other. The inventors have discovered that pigments with excellent light resistance and weather resistance can be obtained from the above, and have thus arrived at the present invention.

The method for obtaining the isoindoline derivative pigment of the present invention is achieved by condensing an isoindolenine derivative and an indanedione compound in an inert solvent.

The isoindolenine derivative used in the present invention has the general formula [wherein A represents an O-phenylene group or 2,3-naphthalene group, and R1 represents an amino group or a halogen atom,
R2 and R3 represent a lower alkoxy group or a halogen atom, and together they represent an imino group.

] As shown in the above, these are isoindolenine derivatives having easily substitutable groups at the 11-position and 31-position, and acid addition salts of the derivatives, such as hydrochloric acid and sulfuric acid.

Among the derivatives shown in the above general formula, 1-amino-3-
Imino-substituted products (including diimino-indoline type tautomers) and acid addition salts thereof 1,3,3-trichlor-substituted products, 1-amino-3,3-dimethoxy-substituted products or 1-amino-3-substituted products - Isoindolenine derivatives such as 3-diethoxy substituted derivatives are inexpensive and advantageous in industrial production. These substituents include phthalimide, 2,3-naphthalimide,
It can be produced by known methods from phthalic anhydride, 2,3-naphthalic anhydride, O-phthalodinitrile, etc. Some of the methods include (1) imides, urea, ammonium nitrate, heating molybdenum ammonium in nitrobenzene to obtain the 1-amino-3-imino-substituted product;
(2) Dinitriles are treated in anhydrous alcohol in the presence of an alkali metal alcoholade to produce 1-amino-3,3-
Obtain a di-lower alkoxy substituted product. (3) React the imide with phosphorus pentachloride to obtain a 1,3,3-trichlor substituted product.

(4) A 1-amino-3-imino-substituted product or a 1-amino-3,3-di-lower alkoxy-substituted product is obtained by reacting a trichlor-substituted product with ammonia or an alkali metal alcoholade. A compound that forms a novel isoindoline derivative pigment by condensation with such an isoindolenine derivative has the general formula [wherein B may substitute up to 4 halogen atoms, O-phenylene group, 2. Represents a 3-naphthalene group or a 1,8-naphthalene group.

] is a known indandione compound shown in the literature.

Specifically, in addition to unsubstituted indanedione compounds such as 1,3-indanedione, 5,6-penso-1,3-indanedione, and perinaphthoindanedione-1,3, halogens such as chlorine, bromine, and fluorine Various halogen-substituted indanediones-1 and 3 in which 1 to 4 atoms are substituted are included.
In the present invention, the isoindoline derivative pigment containing the above-mentioned two components is prepared by mixing 1 molar ratio of the isoindolenine derivative with 2 molar ratios of the indandione compound in an inert solvent at room temperature to 230°C, preferably 60°C to 60°C. It can be easily obtained by condensation at 200°C.

If an asymmetric pigment is desired, equimolar moles of the isoindolenine derivative and the indanedione compound are condensed in an inert solvent to obtain a monomonosubstituted intermediate, and then another indanedione compound is added for further condensation. Obtained by forcing.

In order to obtain highly pure asymmetric pigments, the production of the monomonosubstituted intermediate is carried out at a temperature below 60°C, and the produced intermediate is also isolated before being combined with other indanedione compounds.
It is desirable to carry out the condensation at 00°C. Inert solvents used in such condensation reactions include alcohols such as methanol, ethanol, propanol, butanol, and ethylene glycol, aromatic solvents such as toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and nitrobenzene, and glycol monomers. Ether, formamide, N-N-dimethylformamide, N-
In addition to organic solvents such as methylpyrrolidone, pyridine, quinoline, and acetic acid, isoindolenine derivatives of general formula (1) are
- In the case of 3-diiminoisoindoline, water can also be used as a good solvent, but most preferably N-N-dimethylformamide. The isoindoline derivative pigment obtained by the present invention has a wide range of hues because it can be of a symmetrical or asymmetrical type, and if necessary, it can be used as a pigment for printing inks, paints, and various fibers after being subjected to a known pigment treatment. It can be used for coloring textiles, rubber, synthetic resins, etc., but in particular, the pigment has excellent light resistance and weather resistance, so it is suitable for coloring paints, inks, and synthetic resins for outdoor exposure. Examples will be shown below, and unless otherwise specified, parts are by weight.

Example 1 2.9 parts of 1,3-diiminoinindoline was completely dissolved in 80 parts of 90% acetic acid at room temperature, 7.3 parts of 1,3-indanedione was added thereto, and the mixture was gradually heated to reflux. Let it react for 2 hours.

Then, it is filtered with P at room temperature and washed with methanol and hot water.

On drying, 7.1 parts of a bright yellowish orange pigment of the structural formula are obtained.

This product was converted into N-N-dimethylformamide (hereinafter referred to as DM).
After purification with F), elemental analysis, mass spectrum, and infrared absorption spectrum measurements were performed. The results are shown below. Furthermore, Figure 1 shows an infrared absorption spectrum diagram of this pigment. Elemental analysis value (C26Hl3O4Nl) Nomas vector parent peak: 403 Infrared absorption spectrum indandione νc::o:1705c! n-1(W
), 1660cm-1 (S) aromatic ring: 1565cm-1
(S) νN. , H: 3280cm-1 (W) However, the absorption intensity is (S) strong, (M) moderate, (W)
It is divided into three levels of weak (the same applies below).

This pigment was kneaded with melamine alkyd resin to form a paint, which was then sprayed onto a painted board and then baked.
A painted board colored in a clear yellowish-orange color was obtained. Spray alkyd white paint prepared with titanium white onto this painted board,
When a bleed test was performed by baking at 60° C. for 30 minutes, no bleed occurred. Further, no deterioration was observed after exposure to Sunshine Weather 10-meter for 300 hours, indicating that this pigment had good light resistance.

Example 2 (4) 1,1-dimethoxy-3- in 80 parts of methanol
Add 4 parts of iminoisoindoline and dissolve.

Add 2.8 parts of 1,3-indanedione to the solution and stir at 20-25°C for 6 hours. The precipitated reddish-yellow crystals were filtered with suction, washed with methanol, and then dried in a vacuum at 60°C. The yield of crude product was 5.2 parts, corresponding to approximately 100% of theory. (b) The above product is N-N
-dispersed in 50 parts of dimethylformamide, then 5 parts of
- Add 4.0 parts of 6-penso 1, 3-indandione, and stir at 125 to 130°C for 2 hours.

After cooling to room temperature, suction] P filter and wash using methanol and hot water. On drying, 7.3 parts of a red-orange pigment of structural formula are obtained.

After this product was purified with DMF, elemental analysis, mass spectrum, and infrared absorption spectrum measurements were performed.

The results are shown below. Elemental analysis value (C3OH,5O
4N,) Mass spectrum parent peak: 453° Infrared absorption spectrum νc of indandione = o: 1703 cm-1 (M)
, 1660c1n-1 (S) aromatic ring: 1560c1n-1
(S) A printing ink made by kneading this pigment with varnish has good printing properties and gives printed matter on paper with a clear reddish-orange color.

When this product was exposed to a fademeter for 160 hours, the color did not change. Example 3 l.3 obtained by reacting phthalimide with phosphorus pentachloride
・O- containing 44 parts of 3-trichloroisoindolenine
In 80 parts of dichlorobenzene, 5,6-pensol 1.
8.2 parts of 3-indandione and 2.5 parts of pyridine
of the mixture, gradually heat and stir at 140-150°C for 3 hours.

After cooling to room temperature, filter and wash with methanol and hot water. When dried, 6.8 parts of orange crystals having the structural formula are obtained.

After this product was purified with DMF, elemental analysis, mass spectrum, and infrared absorption spectrum measurements were performed.

The results are shown below. Furthermore, Figure 2 shows an infrared absorption spectrum diagram of this pigment. Elemental analysis value (C34Hl, O4
Nl) Mass spectrum parent peak: 503 Infrared absorption spectrum indandione νo = o: 1700cnL-l (
M), 1660 (m-1 (S) aromatic ring: 1560 cm
-1 (S) This powder is made by coloring polyvinyl chloride orange and heating it at 160°C.
Even when kneaded with two rolls for 15 minutes, it did not change and had good heat resistance.

Further, a migration test was conducted by superimposing a white sheet colored with titanium white on this colored sheet and applying a pressure of 100 y/Cd at 100° C. for 1 hour, but no migration was observed. Furthermore, the colored sheet was exposed to a fade meter for 200 hours, but no change was observed.
Example 4 (a) 2.9 parts of 1,3-diiminoisoindoline is added to 80 parts of ethanol and stirred at room temperature to dissolve.

Next, when 2.9 parts of 1.3-indanedione was added, a slight exothermic reaction caused the mixture to turn into reddish-yellow crystals. After stirring this at room temperature for 5 hours, 60
Stir for 30 minutes at ℃. After cooling to room temperature, filter by suction,
It was washed with methanol and then with water to completely remove excess 1,3-diiminoisoindoline. 60℃
The mixture was dried under vacuum to obtain 5.0 parts of a crude product.

(b) The above product was converted into N-N-dimethylformamide 5
Then, 5.6 parts of 4.5°6.7-tetrachlor-1.3-indanedione were added, and the mixture was gradually heated and stirred at 115-120°C for 1 hour.

After cooling to room temperature, filter with suction F, and wash with methanol and hot water. A reddish yellow pigment with the structural formula when dried 7.8
get the part.

After this product was purified with DMF, elemental analysis, mass spectrum, and infrared absorption spectrum measurements were performed.

The results are shown below. Incidentally, Fig. 3 shows an infrared absorption spectrum diagram of this pigment. Mass spectrum parent peak: 53
9 Infrared absorption spectrum of indandione νc = o:1705cwL-1(
M), 1660cnL-1 (S) Aromatic ring: 1560c
7nH(S), 1540儂-”(S)νc-cl
:7 65cm-1 (W) This pigment colored polystyrene in a bright reddish-yellow color, and no change was observed when this plate was exposed to a fademeter for 500 hours.

Hereinafter, various pigments were synthesized according to the method of Example 4.
The results are summarized in Table-1. Example 16 14.2 parts of 4,5,6,7-tetrachloro-1,3-indandione in 5.4 parts of 5,6-penso-1,3,3-trichloroisoindolenine and 80 parts of 0-dichlorobenzene 1 part and 3.0 parts of pyridine were added.
Stir at 45-155°C for 2 hours.

After cooling to room temperature, it is filtered and washed with methanol and hot water. When dried, 12.5 parts of a reddish brown pigment having the structural formula was obtained.

After this product was purified with DMF, elemental analysis, mass spectrum, and infrared absorption spectrum measurements were performed.

The results are shown below. Furthermore, Figure 4 shows an infrared absorption spectrum diagram of this pigment. mass spectrum parent peak 72
5 Infrared absorption spectrum νc = o:1705cfn-l of Nindan Dione
(W), 1670cfn-1 (M) Aromatic ring: 1565
(Vz-l (S), 1530 cm-1 (S) νc −
cl: 7 80 cm -1 (W) 3 This pigment was kneaded with a melamine alkyd resin to form a paint, which was then sprayed onto a painted board and then baked, to obtain a painted board colored a clear reddish brown.

When a bleed test was conducted by spraying alkali*:tsudo white paint prepared from titanium white onto this coated board and baking it at 160°C for 30 minutes, no bleed occurred. Further, no change was observed after exposure for 500 hours using a Sunshine Weather O-meter, indicating that this pigment had good light resistance.

Example 17 In 80 parts of anhydrous methanol, 4.8 parts of 5,6-penso-1,1-dimethoxy-3-iminoisoindoline and 5
・6-Penso 1・Add 3.9 parts of 3-indandione and stir at room temperature for 4 to 5 hours.

Thereafter, it is filtered and washed with methanol and N-N-dimethylformamide. This wet cake is N-N-
Dispersed in 80 parts of dimethylformamide and 20 parts of glacial acetic acid, then perinaphthoindanedione 1.33.8 parts
and stir at 115-125°C for 2 hours. After cooling to room temperature, filter and wash with methanol and hot water. When dried, 8.8 parts of a reddish brown pigment having the structural formula was obtained.

After this product was purified with DMF, elemental analysis, mass spectrum, and infrared absorption spectrum measurements were performed.

The results are shown below. Elemental analysis value (C, 8Hl9O4
Nl) Mass spectrum parent peak: 553 Infrared absorption spectrum νc=o of l indandione: 1760CTfL-1 (W)
, 1710C11L-1 (W), 1670c! ! l-
1 (M) Aromatic ring: 1570CITL-1 (S), 1
550c1n-1 (S) Printing Ink J, obtained by kneading this pigment with varnish, has good printing properties and gives printed matter on paper with a clear reddish-brown color.

When this product was exposed to a fademeter for 160 hours, the color did not change. Example 18 (a) In 60 parts of N-N-dimethylformamide, 5.
Add 3.9 parts of 6-penso 1,3-diiminoisoindoline and stir at room temperature for 1 hour.

Thereafter, 2.8 parts of 1,3-indandione was added, and the mixture was further stirred at room temperature for 5 hours. The precipitated reddish yellow crystals are f
The mixture was separated, washed with methanol, and dried under vacuum at 60°C to obtain 6.1 parts of a crude product. (5) Disperse the above product in 60 parts of N-N-dimethylformamide, then add 3.9 parts of 5,6-penso-1,3-indanedione,
The mixture was heated at 5 to 120°C and stirred for 30 minutes. After cooling to room temperature, it is filtered with suction and washed with methanol and hot water. When dried, 7.6 parts of a red-orange pigment having the structural formula were obtained.

After this product was purified with DMF, elemental analysis, mass spectrum, and infrared absorption spectrum measurements were performed.

The results are shown below. Furthermore, Figure 5 shows an infrared absorption spectrum diagram of this pigment. Elemental analysis values (C, 4Hl, O4
Nl) Mass spectrum parent peak: 503 Infrared absorption spectrum indandione νc=o: 1755 cm-1 (W)1
720crL-1 (M), 1665Cr11-1 (
S) Aromatic ring: 1560 cm-1 (S), this powder was made by coloring polyvinyl chloride red-orange and heating it at 160°C for 15 minutes.
Even when kneaded with this roll, it did not change and had good heat resistance.

Further, a migration test was conducted by superimposing a white sheet colored with titanium white on this colored sheet and applying a pressure of 100 t/Cd at 100° C. for 1 hour, but no migration was observed. Furthermore, the colored sheet was exposed to a fade meter for 200 hours, but no change was observed.
Hereinafter, a pigment was synthesized according to the method of Example 18.

The results are summarized in Table-2.

[Brief explanation of the drawing]

Figure-1 to Figure-5 are Examples 1, 3, 4, 16, FIG. 3 is an infrared absorption spectrum diagram of the pigment obtained in FIG.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼………………(1) [
In the formula, A represents an O-phenylene group or a 2,3-naphthalene group, R_1 represents an amino group or a halogen atom, and R_
2 and R_3 each represent a lower alkoxy group or a halogen atom, and when taken together, they represent an imino group. ] The isoindolenine derivative represented by the general formula ▲ has mathematical formulas, chemical formulas, tables, etc. ▼……………………(2)
[In the formula, B is O which may substitute up to 4 halogen atoms.
- represents a phenylene group, a 2,3-naphthalene group or a 1,8-naphthalene group. A general formula characterized by condensing one or two indandione compounds represented by ] with an inert solvent, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ [A and B are the same as above. ] A method for producing a novel isoindoline derivative pigment.