DE2321511C2 - Process for the production of isoindolinone pigments - Google Patents

Description

wherein X is a halogen atom, «O or a whole Number from 1 to 4 and R is a direct bond, a divalent aromatic radical or a means divalent heterocyclic radical, characterized in that one Compound of the general formula

CONH-R-HNOC

wherein X, η and R have the definitions given above, heated together with a condensing agent in an inert organic solvent.

2. The method according to claim 1, characterized in that the mixture is heated at a temperature in the range of 60 to 130 ⁰ C.

3. The method according to claim 1, characterized in that at a temperature im Heated range from 70 to 80 ° C.

4. The method according to claim 1, characterized in, that phosphorus pentachloride or phosphorus pentabromide is used as the condensing agent.

5. The method according to claim 1, characterized in that the inert organic Solvents benzene, toluene, xylene, chlorobenzenes, chloroethanes, nitrobenzene, decahydronaphthalene or diphenyl ether is used.

50

55

The invention relates to a process for the production of η isoindolinone pigments.
Known processes for the production of isoindoion pigments are for example behrieben in Swiss patents 346 218,348 496 and 363 980. In these known processes, an oindoline which contains three or more halogen atoms on: m aromatic nucleus is reacted with a primary olyamino compound, see for example

NH,

NH,

NH,

Pigments of the formula are obtained in this way

Cl

HN

\ Cl Cl
/ C.
/ \ vV \ \ / V Cl C. T Il Cl O

In a process described in US Pat. No. 2,537,352, an isoindolin-1-one, which contains no substituent or which contains two substituents on the aromatic nucleus, with a divalent one aromatic diamine implemented. However, the practical implementation of these procedures brings many Problems with yourself. For example, there are many restrictions on the manufacture of isoindolin-1-one; Halophthalimides or o-cyanobenzoic acid esters serving as starting materials are not easy and when a halophthalimide is used as the starting material, it is difficult to obtain the intermediate obtainable in high purity and good yield. Will isoindolin-1-one with a diamine implemented, glacial acetic acid must be present as the reaction medium in the above-mentioned reactions (1) and (3) being. In the reaction (2), a rapid condensation reaction occurs, and thereby it becomes difficult to regulate this implementation.

The invention is therefore based on the object of overcoming the disadvantages of the known methods.

and to create a process in which the [soindolinone pigments can be obtained in high yield, high purity and inexpensively.

The invention relates to a process for the production of isoindolinone pigments, with compounds the general formula

CONH-R-HNOC

CONH,

H ₂ NOC

(I)

wherein X is a halogen atom, η O or an integer from 1 to 4 and R is a direct bond, a divalent aromatic group or a divalent heterocyclic group, are heated together with a condensing agent (dehydrating agent) in an inert organic solvent to give an intramolecular To cause dehydrocondensation. In this reaction, isoindolinone pigments of the general formula

N —R —N

wherein X, η and R have the definitions given above, obtained in high yields and high purity.

The condensing agent used is preferably phosphorus pentachloride or phosphorpene tabromid.

As the inert organic solvent mentioned above, benzene, toluene, xylene, monochlorobenzene, o-dichlorobenzene, trichlorobenzene, dichloroethane, trichloroethane, tetrachloroethane, nitrobenzene, decahydronaphthalene, diphenyl ether, etc. can preferably be used. The amount of condensing agent should be more than 2 molar ratios, and preferably 3 to 4 molar ratios. A temperature above 60 ^° C. is required when heating. A temperature which is above 130 ^° C. is not desirable, since the product is contaminated and the pigment value is reduced. Optimal heating temperatures are in the range from 70 to 3 8G ⁰ C. The reaction is completed in about 0.5 to 4 hours, it is very simple and there are no problems when it is carried out on an industrial scale.

The compound of the formula I, which is used as a starting material for the production of the isoindolinone pigments according to the invention, can be obtained very easily by combining phthalic anhydride or halophthalic anhydride with 1 to 4 halogen atoms in the aromatic nucleus with hydrazine or an aromatic diamine or a heterocyclic diamine in one inert organic solvent using a condensing agent such as phosphorus pentachloride, phosphorus trichloride, thionyl chloride, acetyl chloride, phosphorus oxybromide or acetyl bromide, and then adding ammonia water to the reaction mixture or blowing ammonia gas directly into the reaction mixture. The inert organic solvents used are preferably those which bring about an intramolecular dehydrocondensation reaction.
S As examples of halophthalic anhydrides which contain 1 to 4 halogen atoms in the aromatic nucleus and which can be used as one of the starting materials for the preparation of the compound of the formula I, there may be mentioned
ίο 3-chlorophthalic anhydride,
4-chlorophthalic anhydride,
3,4-dichlorophthalic anhydride,
3,5-dichlorophthalic anhydride,
3,6-dichlorophthalic anhydride,
4,5-dichlorophthalic anhydride,
3,4,5-trichlorophthalic anhydride,
3,4,6-trichlorophthalic anhydride,
3,4,5,6-tetrachlorophthalic anhydride,
3-bromophthalic anhydride,
4-bromophthalic anhydride,

3,4-dibromophthalic anhydride,
3,5-dibromophthalic anhydride,
3,6-dibromophthalic anhydride,
4,5-dibromophthalic anhydride,
3,4,5-tribromophthalic anhydride,
3,4,6-tribromophthalic anhydride,
3,4,5,6-tetrabromophthalic anhydride,
3-fluorophthalic anhydride,
4-fluorophthalic anhydride,
3,4-difluorophthalic anhydride,
3,5-difluorophthalic anhydride,
3,6-difluorophthalic anhydride,
4,5-difluorophthalic anhydride,
3,4,5-trifluorophthalic anhydride,
3,4,6-trifluorophthalic anhydride and

3,4,5,6-tetranuorphthalic anhydride.
As aromatic diamines or heterocyclic diamines which can be used as further starting materials for the preparation of the compound of the formula I, diamines which have hitherto been used as raw materials for the preparation of isoindolinone pigments can be used. Examples of such diamines include o-, m-, p-phenylenediamines, benzidine, o-dianisidine, o-, m-tolidines. 3,3'-dichlorobenzidine, 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-diaminodiphenyl, 2, 6-diaminotoluene, 2,6-diaminopyridine and 2,6-diaminobenzothiazole.
The process for the preparation of compounds of the formula I is illustrated below in the form of a comparative example.

Comparative example

54 g p-phenylenediamine are dissolved in 900 ml of dimethylformamide under stirring at room temperature to the resulting solution are added 300 g of tetra-chlorophthalic anhydride and holds the Temperatui below 30 ⁰ C. The resulting solution dam stirred for 1 hour and with 44 ml Phosphortrichlork dropwise mixed. The mixture is then stirred at the same temperature for 2 hours. 180.5 ml of 28% strength by weight ammonia water are slowly added to the reaction mixture in which the precipitated condensate is suspended. The mixture is stirred at 30 ° C. for 4 hours, a colorless, crystalline precipitate falls out: The mixture is poured into 1 l of ice water

filtered. The colorless residue is suspended again in 2 l of water and ^{stirred at 90 °} C. for 1 hour. It is then filtered hot and then the precipitate is dried. The yield is 329 g. The drawing shows the IR absorption spectrum of the product. The spectrum confirms that the product is a compound of the following structural formula

was sprayed on a tin plate and baked at a temperature of 120 ° C. The sample was examined for their weather resistance, very good results were obtained.

Example 2
15.0 parts of a compound of the structural formula

Cl I CONH ₂
Cl

H ₂ NOC I Cl Cl

The following examples illustrate the invention. Unless otherwise noted, all parts are through expressed the weight.

example 1

13.6 parts compound of structural formula
Cl

CONH

CONH,

NHOC

H ₂ NOC

and 25.8 parts of phosphorus pentabromide were refluxed in 150 parts of benzene and heated and stirred for 3 hours. After cooling, the mixture was added with 10 parts of pyridine mixed, filtered and treated with sufficient benzene, methanol and hot water in the order given washed. The resulting compound was dried and 10.0 parts of a compound with orange color were obtained. A comparison of the known compound by IR spectrum showed that the compound so obtained is a pigment of the structural formula

and 12.5 parts of phosphorus pentachloride are stirred in 100 parts of trichlorobenzene at a temperature of 70 to 80 ⁰ C for 3 hours, cooled and filtered. The residue is washed with sufficient methanol and then with water and dried. 10.7 parts of a reddish yellow compound are obtained. Comparing the compound thus obtained with the known compound by IR spectrum, it is confirmed that the compound is a pigment represented by the structural formula

Cl

Cl

Cl

The pigment was heated with vinyl chloride resin Rolling kneaded, a clear orange-colored film made of vinyl chloride resin was obtained. The pigment itself showed very good heat resistance, migration resistance and weather resistance.

B e i s ρ i e 1 3

The procedure of Example 1 was repeated using 13.9 parts of a compound of the structural formula

represents

A paint obtained by kneading the pigment thus obtained, together with a melamine alkyd resin is sprayed onto a tinplate, and baked at a temperature of 120 ⁰ C for "AusblutungsversTiche" is a color titanium white / melamine alkyd resin to the coated surface of the tin plate sprayed and fired in no case trat.ein bleeding on at a temperature of 140 to 160 ⁰ C.

A color was also made by combining the pigment and a melaniine alkyd resin covered with titanium white m the maximum amount on the pigment, kneaded. This color

Cl

CONH

CONH ₂

NHOC

H ₂ NOC

used; 11.2 parts of a bluish yellow compound were obtained. Comparison with the known Connection by IR spectrum showed that the

bond a pigment with the structural formula CH,

Example 5 8.0 parts of a compound of the formula

^{X /} C

NH HN

\ C C

Il Il

ο ο

Example 4 15.6 parts compound of structural formula

QCH ₃ Cl

CONH

CONH ₂

HNOC

H ₂ NOC

CONH

CONH ₂

and 8.4 parts of phosphorus pentachloride were ^{heated at 60 °} C. and stirred in 80 parts of trichlorobenzene for 1 hour. Then ammonia gas was up to

15 Neutralization was blown in, the reaction mixture was cooled and nitrated. The residue was washed with sufficient ethanol and then with water and dried. A clear yellow color was obtained Connection. The IR absorption spectrum showed that

20 the compound is a pigment of the structural formula

J X

and 12.5 parts of phosphorus pentachloride are heated and at 70 to 8O ⁰ C then stirred for 3 hours with 150 parts of toluene. After cooling, the mixture is mixed with 10 parts of pyridine, filtered and then mixed with sufficient toluene, methanol and hot water in the order given and dried. 10.2 parts of a reddish compound are obtained. Comparison with the known compound by infrared absorption spectrum showed that the compound thus obtained is a pigment represented by the following structural formula

OCH ₃

was.

/
C.
π NH
/ sp i e HN /
C.
Il Il
O Il
0 at 1 6

13.6 parts of a compound of the structural formula

Cl

CONH

CONH ₂

I ei

Cl

In addition, colors were prepared by using the pigments of Examples 1 and 4 and melamine alkyd resin together with titanium white in 20 times A lot of kneading and then the paints were painted on zinc plates and for 2 years, the Weather exposed The results are in labeue 1 listed

Table I.

Hue of
Pigments
Color difference

UE)

example 1

reddish yellow
0.92

Example 2

orange

2.12

Example 3

bluish yellow 3.45

Example 4

red 4.82 and 10.5 parts of phosphorus pentachloride were used during 4 hours in 120 parts of decahydronaphthalene

Heated to 8O ⁰ C 50, then mixed with 3.8 parts of formamide, cooled and filtered. The residue was washed with sufficient methanol and then with hot water. A clear orange compound was obtained. The IR spectrum showed that the

55 bond a pigment of the structural formula

was.

609 682/445

Example 7 10.8 parts of a compound of the structural formula

CONH

CONH ₂

HNOC

H ₂ NOC

Cl

Cl

and 34.4 parts of phosphorus pentabromide was stirred at 12O ⁰ C for 30 minutes in 100 parts of dichloroethane, neutralized, cooled and filtered with ammonia gas. The residue was washed with methanol and then with hot water. A bluish yellow compound was obtained. The infrared absorption spectrum showed that the compound was a pigment represented by the structural formula

egg

Cl

NH

J ν

HN

Cl

Example 8 20.7 parts of a compound of the structural formula

CONH

// V

HNOC

Br

Br I CONH ₂
Br

Br

H ₂ NOC! Br Br

and 12.5 parts of phosphorus pentachloride were ^{stirred at 70 to 8O 0} C for 4 hours in 150 parts of trichlorobenzene, 10 parts of anhydrous sodium acetate were added, and the reaction mixture was filtered and heated at a temperature of 50 to 60 ° C. The residue became sufficient Methanol and then washed with hot water and dried. A clear yellowish compound was obtained. The infrared absorption spectrum shows that the compound is a pigment of the structural formula

Example 9

13.0 parts of a compound of the general structure formula

CONH

CONH,

and 12.5 parts of phosphorus pentachloride were ge at 100 ° C for 1.5 hours in 150 parts of xylene stir, cooled and filtered. The residue was then treated with sufficient xylene, methanol and hot Washed with water in the order given. A yellowish compound was obtained. The IR Absorption spectrum showed that the compound was a pigment of the following structural formula

Example 10

A variety of compounds of the formula

T ■ if? I,. ^{Made from} S ^an g ^smateri alien and used on

same way as described in the above examples

Treated using a variety of isoindolenones received. In the following table II are in column 1

// X

CO-

Br C. \ C. Br Br Br 6o Br I. / \ / \ \ / \ NH HN / V T Ϊ \ / \ / I T \ / C. \ / Br T ? Il T 65 Br O O Br

X "CONH ₂

Components of formula I, in column 2 - NH-R- HN-

*? ^{Fonnel l} ™ ^{d listed in} column 3 that of the pigments obtained

Table II Component of Formula I

Xn CON 1-1,

Cl
Cl I CO-

/ X

Cl I CONH ₂ Cl

the same

like. like. like. like.

the same

the same.

desgL

the same

-NH- R - HN-

- NH-HN-

NH HN-

CH

-NH

-NH

Cl

-NH-

-NH -HN-

HN-

-NH

-NH

C — HN-

Hue of the resulting pigment

Bluish yellow

Bluish yellow

Red

Bluish yellow yellow
Reddish yellow

yellow

Yellow Lichorai Orange

Bluish yellow

yellow

¥

13th

CO--

Xn CONH ₂

CO—

CONH ₂

Cl I CONH ₂ Cl

CO—

Br I CONH ₂ Br

23

continuation

1 511 6y

- NH-R-HN

-NH

A-HN-

-NH

- HN-

14th

OCH ₃

T:

OCH ₃

CH ₃

ΗΝ -

1 sheet of drawings

Hue of the pigment obtained

Reddish yellow

Reddish yellow

yellow

Red

Claims (1)

Patent claims: 1. Process for the preparation of isoindolinone pigments of the general formula CONH, H ₂ NOC the following reaction formulas
NH