DE1444772A1 - Process for the preparation of dyes of the dioxazine series - Google Patents

Description

Process for the preparation of dyes of the dioxazine series

The present invention relates to new dyes of the dioxazine series , processes for their preparation, their use for pigmenting polymeric! organic material and, as an industrial product, the material dyed and pigmented with it.

It has been found that new, strongly colored dioxazine dyes are obtained if a 3,6-bis [aroylamido] 1,4-benzoquinone compound of the general formula I is used

HH -

KH - ₉

in the -

Xl and X ₂ each have a movable one which can be replaced by amino groups

Substituents and

R, and R ₂ each represent an aryl radical,

Simultaneously or in stages with twice the equimolar amount of a primary arylamine or two different primary arylamines whose aryl radicals contain hydrogen or a replaceable substituent in an ortho position to the NH ₂ group and further substituents customary in dyes and / or condensed on in the other positions may contain heterocyclic rings, optionally in the presence of inert ' organic diluents and / or condensing agents,

S09t12 / 09Si

* ORIGINAL BATHROOM

condensed to a dianil of the general formula II,

IiH-COR ₁

" ^H -" * 2. (II)

in the

R ₁ and R ₂ that mentioned under formula I and

A ₁ and A _{2 are,} independently of one another, the aryl radical of the primary arylamines,

and the dianil of the formula II by heating in diluents, optionally in the presence of condensation · = and / or Oxidizing agents to form a compound of the general formula III,

(III)

NH - COR "

in the

R ₁ and R ₂ denote Gexmnta under formula I and A 'and A _{0 ' denote the aryl radicals A 1} and A mentioned under formula II, corresponding ortho-arylene radicals.

The aryl radicals of the formula I ^ symbolized by R ₁ and R ₂ are optionally substituted phenyl = or n> naphthyl radicals, advantageously phenyl radicals «Ri and R ₂ can be the same or different from one another, are advantageous ^ they are identical »It comes into consideration above all? the phenyl =, the 2-, 3- or 4 = methylphenyl ~, the 2 =, 3- or 4 »chlorophenyl =, the 2-, 3- or 4-bromophenyl-, the 2-, 3- or 4- Methoxyphenyl =, the

BATH ORIGINAL

2-, 3- or 4-ethoxyphenyl-, 2-, 3- or 4-nitrophenyl-, the 3,4- or 2,5-dimethylphenyl-, the 3,4-, 2,5- or 2,4-dichlorophenyl-, 2,4,5-trichlorophenyl, 2- or 4-methylsulfonylphenyl, the 2- or 4-sulfamylphenyl, the 2-, 3- or 4-Aeylaminophenyl-, the 2-, 3- or 4-Alkyl- or Arylsulfonylamino-

phenyl, the 3- or 4-carboxylic acid ester phenyl, the 3- or 4-carboxamide phenyl, the 2- or 4- (2'-, 3'- or 4'-l-nitrophenoxy) -phenyl-, 2- or 4-phenylphenyl-, 4- (4'-nitrophenyl) -phenyl-, the naphthyl, nitronaphthyl or chloronaphthyl (1) or (2) radical.

Particularly pure and solvent-resistant and therefore preferred dioxazines of the formula II are those in which R ^ and R _{2 represent} a phenyl radical, but the purest hues are obtained when R ^ and R _{2 represent} the o-methylphenyl or o-chlorophenyl radical .

The aryl radicals symbolized by A ₁ and A «in formula II denote optionally substituted phenyl or naphthyl radicals, advantageously phenyl radicals. They can be the same as or different from one another; the two aryl radicals are advantageously identical. As replaceable substituents in the o-position to

NH groups contain A, and Ap, for example, an ether group.

Suitable ether groups are, for example, alkoxy, cycloalkoxy, aralkoxy or, above all, the easily cleavable aryloxy groups, such as the phenoxy, methylphenoxy or chlorophenoxy groups. In addition to these replaceable substituents in the o-position to the NH group, A ₁ and A _{2 can be used} in dyes which are customary 909812/0951

BATH ORIGINAL

preferably non-ionic substituents, or also condensed contain heterocyclic rings.

A, and Α «in the formula II, or in A ^" and A ^ ** in the formula III, for example, aliphatic, cycloaliphatic, araliphatic ^ or aromatic groups, ether groups such as alkoxy, hydroxyalkoxy, aralkoxy - or aryloxy groups, - where the aryl radicals of the latter two can be unsubstituted or substituted, for example with methyl, chlorine, bromine, methoxy or carboxylic acid ester groups, also thioether groups, such as the alkyl mercapto or aryl mercapto group, halogen, such as chlorine or bromine, the nitro *, the cyano or trifluoromethy group, the primary amino group, optionally N-substituted carboxamide and sulfonic acid amide groups, carboxylic acid ester, sulfonic acid aryl ester, acyl, alkylsulfonyl, arylsulfonyl and acylamino groups, where " Acyl "is to be understood in the broadest sense and is, for example, a carbacyl, carbonic acid monoester, carbamyl, thiocarbamyl or a 1,3,5-triazinyl radical, but preferably a carbacyl radical, b means included.

A, and Ap or A ^ ¹ and Ag ^1, for example, contain an indole or furan ring as condensable heterocyclic hinge.

Derived A ₁ and Ag in the formula II from 4-alkoxyanilines from, to obtain pure i red dioxazine dyes of the formula III they are derived from 4-Phenoxyanllinen from, one arrives at particularly pure, red, and therefore preferred inventive Dioxazinfarbstof fen .

R ₁ and R ₂ is a phenyl group, an o-chlorophenyl or o-methylphenyl group, then, draw red shades those pigment color material = · by very interesting from above in which A

§09812 / 0951

U44772

and Α «denote phenylene radicals in the p-position to the nitrogen atom of the oxazine ring by a lower alkoxy group, the ethoxy usually giving a purer shade than the methoxy group, or substituted by an optionally substituted phenoxy group are, and optionally contain carboxylic acid esters, carboxamide, acyl groups or halogens in the p-position to the oxygen atom. It is therefore a further advantage of the present invention that you can use simple substituents to create difficult-to-dissolve, migration-

and coated red dyes of the dioxazine series. The 3,6-bis [aroylamido] -1,4-benzoquinone compounds used as starting materials of the formula I are known in some cases. For example, they can be produced by oxidation of finely powdered 3,6-bis [aroylamido] -1,4-bis-ethoxybenzene in Glacial acetic acid with nitric acid. From the 3,4-bis [aroyl-

amido] -l, 4-benzoquinone is formed by bromination in chloroform, 2,5-di-bromo-3,6-bis- [aroylamido] -l, 4-benzohydroquinone '.'"· .. and by subsequent oxidation with nitric acid one then arrives at 2,5-di-bromo-3,6-bis- [aroylamido] -l, 4-benzoquinone.

The dianils of the formula II according to the invention used are new. They are obtained, for example, by reacting a 2,5-dihalo-3,6-bis [aroylamido] -l, 4-benzoquinone with primary arylamines which contain hydrogen or a _{mobile substituent in the o-position to the NH 2} group, for example in Ethylene glycol \ monoethyl ether or an aromatic hydrocarbon,

, 9098 12 / 095.1 _{BAD 0R} , _ONE

such as benzene, chlorobenzene or dichlorobenzene, optionally in the presence of an acid-blunting agent ₃ such as alkali hydroxide, for example sodium hydroxide, or alkaline earth oxide or hydroxide, for example magnesium oxide, alkali carbonate, an alkali salt of a lower fatty acid, for example sodium acetate or tertiary bases, such as, for example Triisopropanolamine, methyldicyclohexylamine or triisobutylamine.

The D + aniles of the formula II prepared in this way can before their Conversion into the dioxazine compounds of the formula III are isolated The substances used can be converted directly into the dioxazine dyes of the formula III without isolating these dianiles.

The condensation of the compounds of the formula II to the Dioxazi dyes of the formula III is preferably carried out in inert organic solvents, optionally in the presence of acids, acid-releasing or acid-forming compounds, if necessary in the presence of oxidizing agents, with heating »preferred is the thermal ring closure in high-boiling solvents, optionally with the use of oxidizing agents, but in the absence of acidic condensing agents, since the latter is im In contrast to condensations with chloranil, the yields are generally poorer. »Starting materials with phenoxy groups than Replaceable .Substituenten are preferred in the thermal ring closure because these are generally easier to split off are as for example alkoxy groups.

909812 / 09S1 bad obsinal

Suitable inert organic solvents include optionally halogenated aromatic hydrocarbons of the benzene or naphthalene series, z, .BS xylenes, nitrobenzene, di- and trichlorobenzene, naphthalene, and a ~ Chlorna.phthaiin, alcohols and their esters, such as ethanol, propanol _s benzyl alcohol, Ethylene glycol, ethylene glycol methyl, ethyl or phenyl ethers, and their acetates, benzoates or phthalates.

Suitable acids are, for example, concentrated inorganic μ

Oxygen acids, such as sulfuric acid or polyphosphoric acids, as well strong organic acids such as di- or trihaloacetic acids.

Examples of acid-releasing or acid-forming compounds are, in particular, the acid halides of carbon or Sulphonic acids, such as banzoyl chloride or 4 = methylbenzenesulphonic acid chloride, also thionyl chloride, phosphorus pentachloride or metal chlorides such as aluminum chloride.

Suitable oxidizing agents are, for example, atmospheric oxygen and aromatic nitro compounds, namely nitrobenzene or Nltrobenzenesulfonsäuren called.

The choice of condensing agents and conditions is directed see in each case the starting compounds used.

For example, dianils of the formula II, in which A ₁ and A ₂ each contain an ether group in o-position to the NH group, are expediently converted to 100 to 300 * in a mixture consisting of an inert organic solvent and an acid-binding agent. C, preferably heated to 150 to 260'C.

909812/0951

• AD

Dianiles of the formula II, in the A, and A «in the 2- and 4-positions to the NH group there is one ether group each, preferably one optionally containing substituted phenoxy group can be obtained by heating in inert organic solvents at relatively low temperatures without further additives converted into the dioxazine compounds of the formula III.

The dianiles of the formula II, in which A ^ and Ag each have one in the o-position

ment to the NH group containing a hydrogen atom aromatic radical mean, condensation is advantageously carried out in an organic solvent in the presence of an oxidizing agent, and optionally an acid donor.

The dioxazine compounds of the formula III according to the invention mostly almost crystallize in the hot reaction mixture completely and in pure form. They show the characteristic Properties of the dioxazine dyes, e.g. blue solution color in concentrated sulfuric acid, metallic luster of the crystals and fluorescence in 1,2-dichlorobenzene. They are by filtering off isolated and further purified by washing out the precipitate with organic solvents and aqueous acids or bases.

§09812 / 0951

- y - i 444 / / £

Ede dioxazine dyes that are sparingly soluble in organic solvents can be used as pigment dyes. For the use as pigment dyes, they are advantageously in a. - brought finely dispersed form. The fine division takes place purposefully. Badly by grinding in the presence of grinding aids, such as inorganic or organic solvents that can be removed again Salts, and optionally additional grinding aids, such as organic Solvents, acids or bases.

Organic solvents which are solid or liquid at room temperature can be used. One grinds, for example, those from the reaction mixture isolated and dried pigment dyes with dehydrated calcium chloride or with sodium sulfate or sodium chloride

»In the presence of aliphatic or aromatic, optionally chlorinated and / or nitrated hydrocarbons, such as cyclohexane, benzene, toluene, naphthalene, mono-, di- or trichlorobenzene, tetrachloroethane, or nitrobenzene ₃ also lower aliphatic ketones, such as z _o B _D acetone or lower aliphatic monoalcohols, for example methanol, ethanol, methoxy. or ethoxyethanol, or nitrogen compounds, such as dimethyl or.

', Diethylaniline, quinoline or dimethylformamide, in some The pigments can also be precipitated by grinding with organic solvents, without the addition of salts,

<· Refine. After grinding, the auxiliaries are removed, o- - ■

^ inorganic salts, for example, dissolved with water and organic> see auxiliaries, if necessary, removed by distillation or with * jj * steam.

_ * Finely dispersed, orange, red, burgundy-colored, blue and purple pigments of remarkable color strength and purity, giving way to a softer texture compared to the raw products and have a higher color strength. You are for pigmentation

BATH ORIGINAL

of varnishes, rubber, lacquers, e.g. stoving lacquer and Plastics such as polyvinyl chloride can be used. They are also very suitable for making printing inks for the Paper printing, as well as for dyeing viscose and cellulose materials in bulk »The orange, red, red-brown, corinth-colored, violet and blue colorations and prints are characterized by a high color strength, as well as by good solvent, overcoating, migration, rubbing and lightfastness, and heat resistance.

Further details can be found in the following examples. Therein parts mean unless otherwise is expressly noted, parts by weight. The temperatures are given in degrees Celsius. Parts by weight behave

• 3
to parts by volume like g to cm.

909812/0951

IAD

At a ni el 1

20.16 parts of 2,5-dibromo-3,6-bis-ibenzoylamino) -1 _> 4-benzochinone _i . 12.3 parts of 1-amino-2,4-dimethoxybenzene and 13.1 parts of anhydrous

Sodium acetate is heated for 30 minutes in 250 parts by volume of 1-chloronaphthalene at 200-210 * with stirring. The dark red suspension is the residue of ethanol, water, a mixture of Aethylengiykol "monoäthylather and dilute sodium hydroxide solution filtered at 140" ^ water and finally washed with acetone and dried to give _.13} 7 parts of a red-brown crystalline product of the above formula For the purpose of fine division it is mixed with sodium chloride, sodium sulphate or anhydrous calcium chloride, in the presence of a small amount of the petroleum fraction boiling at 180-220 *

ο ground. After removing the salt and the old solution ice

^ you get a red pigment of high color strength, good light,

^ Heat, varnish and migration fastness.

cd If one replaces the 2,5-dibromo-3,6-bis «(benzoylamino) ~ l, 4 ·

~ * Benzoquinone by 21.4 parts of 2,5-dibromo-3,6 "-bis" i2 = ^l -msthylbonzoylamino) -l, 4-benzoquinone or by 21.4 parts of 2,5-dibromo-3,6-bis - (4 ^l -methylbenzoylamino) -1, 4-benzoquinone or by 22.9

BATH ORIGINAL

Parts of 2,5-dibromo-3,6-bis- (2'-chlorobenzoylamino) -1, 4-benzoquinone and otherwise proceeding in the same way as above, one also produces red pigments, namely 2,6-dimethoxy-9 , 10-bis (2'-methyrbenzoylamino) triphendioxazine, or 2,6-dimethoxy-9,10-bis (4'-methylbenzoylamino) triphendioxazine or 2,6-dimethoxy-9,10-bis - (2'-Chlorbenzoylamino) triphendioxazine ₀ These pigments have properties similar to those of 2,6-dimethoxy-9,10-bis (benzoylamino) triphendioxazine.

The 2,5-dibromo-3,6-bis (benzoylamino) -1,4-benzocWnone used are they are orange-brown compounds that are sparingly soluble in common organic solvents are. They are oxidized by the corresponding 3,6-bis (benzoylamino) 1,4-dimethoxybenzenes with nitric acid in glacial acetic acid, subsequent bromination of the resulting 3,5-bis- (benzoylamino) -1,4-benzoquinones with bromine in chloroform, with 2,5-dibromo-3,6-bis (benzoylamino) -l, 4-hydroquinones arise - and get another treatment with nitric acid in glacial acetic acid.

Example 2

Cl

co

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17.2 parts of 2,5-dibromo-3,6-bis (2 '»oleobenzoylamino-) - 1,4- benzoquinone, 10.8 parts of l-amino, 2,4-diethoxybenzene and 9.8 parts of anhydrous sodium acetate during 30 minutes in 200 volume * = parts of 1-chloronaphthalene at 200 = 210 "is heated with stirring" The resulting dioxazine is isolated as in example. 1 is obtained 12j6 parts of red-brown crystals of green gloss "'After finely dividing by grinding with inorganic salts such as calcium 'chloride, one obtains a blaust'ichig red pigment of high color strength λ, very good light, heat =, lacquering and migration fastness, and especially of very pure tone "

In Table I below are similar color strength and real dioxazines listed _s the outputs benzoquinone = compounds of the formula I and have been l ~ Amino = 2,4-diethoxy ~ benzene prepared according to the method described in the above example "The column 1 the Substituents R-, and R _{9 of} the benzoquinones used again, the column 2 indicates the color of a polyvinyl chloride film colored with the dioxazine pigment.

BATH ORIGINAL

909812/0951

Tabel

H44772

No. R ₁ and R ₂ in formula I. Color in polyvinyl chloride =
foil 1 yellowish red 2 bluish red 3 -O ⁰ S yellowish red OH 4th bluish red 5 yellowish red ι
6th -Q-ci
Cl bluish red 7th -O-CDL yellowish red

Example 3

GO

KE

ft

OO

9 O <T8 1 2 / O 9 5 1

BAD OWSSNAL

Parts of 2,5-dibromo-3,6-bis (benzoylainino) -1,4-benzoquinone, 18.3 parts of 1-amino-2,4-bis (2 ° -methylphenoxy) -benzene and 9.2 parts anhydrous sodium acetate are divided into 200 volumes of 1-chloronaphthalene for 30 minutes at 200-210 * heated with stirring. The red dioxazine compound formed is isolated and purified as indicated in Example 1. 11.5 parts of pure 2,6-Bie- (2 ^l -methylphenoxy) -9,10-bis (benzoylamino) -trlphendioxazine are obtained in the form of red-brown crystals with a green gloss. A red color is obtained by grinding with inorganic salts

Pigment of high color strength, very good fastness to light, heat, varnish and migration. Red dioxazine pigments of similar good properties are obtained if, instead of 2,5-di- bromo-3,6-bis (benzoylamino) -l, 4-benzoquinones, 17.2 parts of 2,5-dibromo-3,6 -bis- (2'-chlorobenzoylamino) -1,4-benzoquinone or 17.2 parts of 2 , 5-dibromo-3,6-bis- (4 ³ -chlorobenzoylamino) ° 1,4-benzoquinone or 21.4 parts of 2 , 5-dibromo-3,6-bis (2 ³ , 4 ^e -dichlorobenzoylamino) -1> 4 benzoquinone or 17.8 parts 2,5-dibromo-3,6-bis (2 ^t -methylbenzoyl-amino) no) -1, 4-benzoquinone or 17.8 parts 2 _s 5 = dibromo-3 ₅ 6 »bis (4'-methyl- t

benzoylamino ^^ benzoquinone or 18.7 parts of 2,5-dibromo ~ = 3,6-bis- (3 ^ 4 ^ ^t -dimethylbena lamino> = Q _s 4 '- benzoquinone "or 18.8 parts of 2,5-dibromo -3,6-bis- (2 ³ -methoxybenzcsC ^ aiinoKl ^ benzoquinone or 18.8 parts of 2,5-dibromo-3,6-bis- (4'-methoxyben2X ^ 16mino> = 1,4 «benzoquinone or 17 , 5 parts of 2,5-DihiT; ro-3,6-bis- (3'-nitrobenzoylamino) »1,4-benzoquinone or 17.5 parts of 2,5-dinitro-3,6-bis (4'- nitrobenzoylamino) -l, 4-benzoquinone used and otherwise the same procedure as indicated in the above example.

909812/0 951

Building

The 2,5-DinItro-3,6-bis- (3 ⁵ -nltrobenzoylamino) -1,4-benzoquinone is produced by oxidation and nitration of the 3 _s 6-bis (benzoylamino) -1,4-bis-methoxybenzene and the 2.5 <= dinitro-3 ₃ 6 "-bis- (4 '= nitrobenzoylamino) -1, 4-benzoquinone by oxidation and nitration of the 3,6-bis (4 ^s -nitrobenzoylamino) -1 _s 4 -dimethoxybenzene with made from a mixture of concentrated nitric acid and concentrated sulfuric acid «

Example 4

OO

NH

17.2. Parts of 2,5-dibromo-3,6-bis = (2 ⁱ ~ chlorbenzoyiainino) -l, 4-benzoehinon, 16.65 parts l-amino-2,4-bi £ - (phenoxy) benzene and 9.2 ~ Parts of anhydrous sodium acetate are heated for 1 hour in 250 parts by volume of 1-chloronaphthalene at 200 = 210 "with stirring. The resulting dioxazine compound is isolated as in Example 1. 15.8 parts of red-brown crystals are obtained which, after grinding with CaCl ₂ © in pure red pigment of high color strength and very good light, heat, varnish and migration fastness.

Valuable red pigments with similarly good properties are also obtained if the above example is otherwise identical Method of operation in place of the l-amino-2,4-bis- = iphenox $> enzols

909812/0951

18.3 parts of 1-amino "2,4-bis (4 ⁱ -niethylphenoxy) - 'benzene or' 18.3 parts of 1-amino-2,4-bis (3 '~ methylphenoxy) benzene or 20, 8 parts of l-amino- ^ 4-bis- (4 "-chiorphonoxy) -benzene or 20.2 parts of l-amino-2,4-bis- (4 ^t -methoxyphenoxy) -benzene or

19.7 parts of l-amino-2,4-bis (2% 6 ³ -dimethylphenoxy) benzene or

22.8 parts of 1-amino-2,4-bis (phenoxy) '5-benzoylbenzene or

24.2 parts of 5-amino-2,4-bis (4 ^! -Chlorophenoxy) -1-benzoic acid methyl

ester or

27.9 parts of 5-amino-2,4-bis (phenoxy) -l-benzoic acid-2 ', 5'-dichloro

anilide or

18.7 parts of 1-amino-2j4-bis (phenoxy) -5-chlorobenzene or 18.7 parts of 1-amino-2,4-bis (phenoxy) -3-chlorobenzene are used and the procedure is otherwise identical to that given in the example .

Example 5

10.08 parts of 2,5-dibromo-3,6-bis (benzoylamino) -1, 4-benzoquinone

116.15 parts of 2-methoxyaniline and 4.1 parts of anhydrous sodium

* < acetate are poured in 150 parts by volume for 6 hours o o

Dichlorobenzene heated to 120 *. The formed dianil becomes

"" * filtered off cold and the residue washed with o-dichlorobenzene, ethanol, water and acetone and dried. 10.8 parts of gray-brown, crystalline dianil are obtained.

BATH ORIGINAL

By heating the Dianils for 1 hour in 200 [parts by volume of 1-chloronaphthalene at 230 "is carried out under thermal ring closure to form the corresponding Dioxazinverbindungο arises initially an orange-red solution j from which once the dioxazine compound in the form of fine needles is eliminated. It is used in 150 * suctioned off with AethyIglykolmonoäthylether and acetone and dried. 6.5 parts of orange-red crystals are obtained, which, by grinding with inorganic salts, give an orange pigment of very good fastness to solvents, varnishes, migration and light.

Example 6

H ₃ CSO ₂

Parts 2, 5-dibromo-3,6 = Ms ~ (benzoylamino) -lj4-benzoquinone, 15.8 parts of 1-amino-2-phenoxybenzene-5 = methylsulfone and 9.2 parts anhydrous sodium acetate are heated in 200 parts by volume of 1-chloronaphthalene to 120-130 * for 20 minutes, during which the suspension has a dark discoloration. The dianil thus formed is then heated to 200 ° without isolation and for 1 hour kept at 200 * with stirring.

BATH ORIGINAL

H44772

The dioxazine formed is isolated and purified as indicated in Example 1. 9.3 parts of orange-brown crystals are obtained which, after grinding with CaCl _{2, give} a strongly colored, orange pigment of very good fastness to migration, varnish and heat, and of good fastness to light .

'In the following Table II properties are summarized similarly dioxazines, which have been prepared from ä Dianilen of the general formula II according to the method described in the above example. The column 1 shows the substituents -NH-A ^ and -NH-Ag of the dianil used, the column 2 shows the color of a polyvinyl chloride film colored with the finely divided dioxazine pigment.

BATH ORIGINAL 909812/0951

Table II

.-NH-A ₁ and -NH-A ₂ in formula II colors in polyvinyl chloride film

-MH-O KI

W ₅

-JiH-O-CH O

Cl

egg

Cl -NE-O-CONH-O

^ O

-DH-QhHHCOCH,

909812/0951 orange

orange-red orange-red

orange-red bordeaux

reddish brown reddish blue

reddish brown

violet

reddish purple

ORfGlNAL INSPEGTED

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Example 7

30.24 parts of 2,5-dibromo-3,6-bis (benzoylamino) -r, 4-benzoquinone, 25.2 parts of 3-amino-N-ethylearbazole and 9.8 parts of anhydrous sodium acetate are added for 30 minutes at 200-210 ", then heated for 6 hours at 220 * in 500 parts by volume of 1-chloronaphthalene with stirring. The dark suspension is filtered off at 150 * and the residue is purified as indicated in Example 1» This gives 12.9 parts of a dioxazine of The above formula, which after salt grinding gives a pure violet pigment of very good light, heat, varnish and migration fastness .

example 8th

CO

NH

909812/0951

BATH ORIGINAL

10j8 parts of 2,5-dibromo-3,6-bis (benzoylamino) -1,4-behzochinone, 12 parts of 1-amino-2,5-diethoxy-4-benzoylaminobenzene and 7.65 parts of triisopropanolamine are added for 4 hours refluxed in 150 parts by volume of chlorobenzene »The resulting. Precipitate is filtered off hot, ₃ washed with ethanol and water and dried. "14.4 parts of gray-violet, crystalline Dianilo This product dissolves in a hot mixture of ethylene glycol monoethyl ether and sodium hydroxide solution with a yellow-brown color"

For conversion into the dioxazine compound is the Dianil for 40 minutes in 200 parts of o-dichlorobenzene at 175 "heated The suspension formed is filtered off at 150 ° and the green crystalline residue with ethanol and acetone gevasehea" is obtained 12 parts of a _dioxazine} which by grinding with inorganic salts such as CaCl ₂ or Na ₂ SO _4, a violet pigment with very good light, overcoating ", heat and migration fastness results"

If the ring closure is carried out in the presence of 10 parts of benzoyl " When carried out chloride, only 6 parts of the Dioxazinver = are obtained binding"

In the following Table III the hues of polyvinylochloride films colored with similar dioxazine pigments are compiled (column 2). These dioxazine pigments were produced from dianils of the general formula II according to the method described in the above example. The column 1 shows the substituents -NH-A- and -NH-A _{2 of} the dianil used.

9 0 9 81 2 / Ö Ö 5 1 _gÄD

- 23 table

»0. 6th -NH-A ₁ and -NH-A ₂ in formula II ■ I. 1 Faibvä m polyvinyl "
chloride foil I. 1 7th OCH ₃ 95 violet ' OCH ₃ , 2 -heÄeco-O violet 0 (S ₃ 3 OCH Cl blue
I.
1 4th j
blue ! OCH ₃ 5 1
1
violet ^OC 2 ^H 5 blue 0O ₂ H ₅
"Art \ /" "AIIvU" ^ / ^^ ** r * violet 909812 / 0

ORIQ | _Nal

HU 7

Example 9

16.6 parts of 2,5-dibr.om-3 "- (2 ^Q -chlorobenzoylamino) -6- (2 ^l -mötliylbenzoylamino) -1,4-benzo-quinone, 10.8 parts of 1 ° amino-2 _s 4 -diethoxy · = Benzene and 9.8 parts of anhydrous sodium acetate are heated for 30 minutes in 200 parts by volume of chloronaphthalene at 200-210 "with stirring. brown crystals with a greenish sheen. After fine division by grinding with salt, a bluish red pigment with properties similar to the pigments described in Example 2 is obtained

The 2,5-dibromo-3 ° (2 · »chlorobenzoylamino) -6- (2 ^s -methylbenzoylainino) = 1,4-benzoquinone was obtained by oxidation with nitric acid in glacial acetic acid of 3 ~ (2 ^! = Chlorobenzoylamino) -6- ( 2 ^{ -methylbenzoylamino) - = 1,4-dimethoxybenzene sum corresponding 1,4-benzoquinone and subsequent bromination and oxidation hergastell "

9098 12/095

BAD ORiQIHAL

U44772

Example 10

C O

KH

co

CO

12.08 parts of 2,5-dibromo ~ 3,6 ~ bis = (l ³ ~ naphthoylamino) "l, 4" benzoquinone, 12.2 parts of l-amino ~ 2,4 ° to 2 ^ ^J ~ methylphenoxy) = be :: zGi Xi η d 6.56 parts of anhydrous sodium acetate are heated for 30 minutes in 150 parts by volume of 1-chloronaphthalene at 200-210 * with stirring. The red crystalline dioxazine compound formed is filtered off at 80 "and worked up as in Example 1 is obtained 4.1 parts of pure 2,6-bis = (2 ⁰ «= methyl = 'pheno3cy) -9,10-ibis ° (1 ⁱ -naphthoylamino) = triphenedioxazine. After grinding with calcium chloride, a strong red pigment of pure color is obtained Color and good varnish and migration fastness.

This gives a bluish red pigment of excellent Migrationseehtheit if, instead of the (2 ^l -m * thylphenoxy) l-amino-2,4-laii- "benaoll5 _i 8 parts of 5-amino-2,4-bis- one ( phenoxy) benzoic anilide and otherwise proceed in the same way as indicated in the example »

909812/0951 _{BADOR | G | NAU}

HAA772

Example 11

11.45 parts of 2,5-dibromo-3,6-bis (2'-chlorobenzoylamino) -1, 4-benzoquinone, 13.6 parts of 1-amino-2,4-bis (4'-methylphenoxy) -5-chlorobenzene and 9.8 parts of anhydrous sodium acetate are • in 150 parts by volume of 1-chloronaphthalene for 1 hour 210 - 215 ° heated with stirring “The resulting dioxazine compound is isolated as in Example 1. 8.6 parts are obtained Brick-red crystals which, after grinding with anhydrous sodium sulfate in the presence of a little xylene, are very pure bluish red pigment of very interesting shade, of high color strength and good light, heat, overcoating and Migration authenticity.

A bluish-tinged red, but yellower pigment with similarly good properties is also obtained if one of the above Example with otherwise the same procedure instead of 1-amino-2,4-bis (4'-methylphenoxy) -5-chlorobenzene 8.6 parts of 1-amino-2,4-diethoxy-5-chlorobenzene used and otherwise proceed in the same way

909812/0951 as specified in the example.

BATH

= ■ 27 ^

Example 12

To produce a color for graphic purposes, 2 parts of the substance according to Example 8 from 1 "> Amino-2,5-diethoxy ~ 4 = benzoyl ~ aminobenzene and 2,5 ~ dibromo ~ 3.6 <= bis ° (benzoylamino) ~ l _i 4 milled ~ benzo "quinone produced and with salt pigment with 36 parts of alumina hydrate, 60 parts of linseed oil of medium viscosity and 0.2 parts mixed Kobaltlinoleat on the three-roll mill · and triturated .. with this color paste violet prints can of high color strength and good fastness to light be generated*

Example 13

0.6 parts of the ground according to Example 4, from l ~ _Affiino-2} 4 => bisphenoxy-benzene and produced with salt pigment are mixed with 67 parts of polyvinyl chloride., 33 parts Dioütylphthalat _ä 2 parts of dibutyltin dilaurate and 2 parts of titanium dioxide ver ~ and during 10 - 15 minutes at 140 "rolled", red polyvinyl chloride films of very good migration and lightfastness are obtained »

Example 14

J ₀ 10 parts of titanium dioxide, 35 parts of a solution of a 6Obigen cd modified urea alkyd resin in xylene / butanol Isl _s .10

- * Parts of turpentine oil and 5 parts of xylene are mixed with 2 parts of the Q according to Example 2 from l-amino-2,4 = diethoxybenzene and 2,5 ~ dibromo-

cn 3,6-bis (2 ^: -chlorobenzoylamino) -l, 4 = ° benzoshincn

The pigment is ground in a ball mill for 48 hours. When you pour this colored lacquer onto aluminum foils ϊ and burns in at 120 * for an hour, you get '

BATH ORIGINAL

1UA 7

Paintwork that is outstandingly pure bluish red hue and very good light = ·, heat and Distinguish overpainting ",

β η η _η <■ ■ 909812/095

Claims (1)

Claims U44772 (ly process for the preparation of dyes of the dioxazine · = series, characterized in that there is an S ^^ bis ^ aroylamido] -1,4-benzQquinone compound of the general formula I. x " NH - ₂ in the - XL and Xg 3® have a mobile substituent which can be replaced by amino groups and R, and Rp each denote an aryl radical, simultaneously or in stages with twice the equimolar amount of a primary arylamine or two different primary arylamines, the aryl radicals of which in an ortho-position to the NH ₀ group contain hydrogen or a replaceable substituent and others in the remaining parts , can contain substituents customary in dyes and / or fused-on heterocyclic rings, optionally in the presence of inert organic diluents and / or condensation agents, condensed to a dianil of the general formula II, NH- CQR ₁ H γ 0 A ₂ -NH γ 0 (II) NH- COR " Zr, * , »« 88 12/0 96 1 BADOKG ₁ NAL and Rg that mentioned under formula I and H44772 A ₁ and Α «, independently of one another, denote the aryl radical of the primary arylamines, and the dianil of formula II by heating in diluent ^ optionally in the presence of condensation and / or oxidizing agents ring closes to a compound of the general formula III, (in) in the R, and Rp that mentioned under formula I and Α, ¹ and A2 ^g denote the ortho-arylene radicals corresponding to the aryl radicals A mentioned under formula II and A2, mean «2 ο embodiment of the process according to claim I ₅ thereby characterized in that one is the condensation of the starting components and the ring closure at the same time by heating in the presence of acid-binding agents to temperatures of 150 * to 260 * C performs. 3. The method according to claims 1 and 2, characterized in that that one uses primary arylamines, which are in an otho division for NHg-Gruppe'as replaceable substituents contain an ether group. 4. Process according to claims 1 to 3, characterized in that one uses ¹ primary aryl amines containing substituted in an ortho ° abutment condition for NHg group as a substituent replaceable an optionally "phenoxy group. 909812/0951 5. The method according to claims 1 to 4, characterized in that twice the equimolar amount of a primary arylamine used. 6. Process according to Claims 1 to 5, characterized in that. that the primary arylainin is 2,4-di-ethoxy = l-amino = benzene used. 7. Process according to Claims Γ to 5, characterized in that the primary arylamine is optionally ring-substituted 2,4-Di-phenoxy-l-aminobenzenes used <, 8. The method according to claims 1 bio 7, characterized by that one uses benzoquinones of the formula I, in which R, and Rp identical residues of the benzene series mean o 9. The method according to claims 1 to 8, characterized in that that one uses benzoquinones of the formula I, in which p is the o-chlorophenyl group «, o · Around IiH- cm, Around (III) in the Rp an aryl radical and ""
A, ¹ and Ap 'each represent an ortho-arylene radical ^ x ^ it may contain fused heterocyclic rings in dyes. ^ \ 11. Process for coloring and pigmenting polymeric organic Material, characterized by the use of dyes of claims 9 ...,; ■ _ ■ £ Q-9 812/0951 BATH ORIGINAL