DE1794317A1 - Nitro dyes of the acridone series - Google Patents

Description

Dr. F. Zumstein jun. _ _Λ ο- ₀ η. _Τλ · Patent Attorney · ^D 1-2j28 "Di.V

JR Geigy i.6. Basel / Switzerland Nitro dyes of the acridone series [elimination from patent (Pat.Anm. P 15 69 775.3-43)]

The present invention relates to nitroacridone dyes of the formula I,

(D

in the

R is an alkyl containing not more than 18 carbon atoms

or alkenyl radical;

an alkyl radical containing at most 12 carbon atoms, by a hydroxyl, lower alkoxy, phenylalkoxy, phenoxy-alkoxy, phenoxy, cyclohexyl, phenyl, lower Alkoxycarbonyl, cyclohexyloxycarbonyl, alkoxyalkoxycarbonyl, lower alkanoyl, or an optionally is substituted by a lower alkyl, a cycloalkyl or a benzyl group;

a cyclohexyl radical;

one through a methyl or methoxy group or halogen

substituted ht-nzyl group;

a phenyl radical, which is optionally tuenten by at least one c \ ^ ΐ the following: halogen, tri. fl. normet hy 1, nitro, cyano, alkyl, lower alkoxy, lower] kylsulfonyl, lower AlV-oxycarbonyl, carbainoyl, M'.Cid & ralkylcarbainoyl,

BATH ORIGINAL 1 0 9 8 1 ß / I 9 6 3

Diniederalkylcarbamoyl or an optionally by one lower alkyl or alkanoyl substituted araino group is substituted; or

denotes a naphthyl radical, and in which the ring A is unsubstituted or a lower alkyl or lower alkoxy group, has a nitro group, an amino group or halogen or is condensed with a benzene nucleus and the ring B is not further substituted or substituted by a halogen is.

The new dyes of the formula I are prepared by, for example, an acridone compound of the formula II,

(ID

in the

X represents fluorine, chlorine or bromine and the above applies to A and B, with a mercapto compound of formula III,

HS-R (III)

in which R has the meaning given above hac, if appropriate reacted in the presence of an acid-binding agent or with a metal salt of a mercapto compound egg formula III. The reaction of the acridone compound of the formula II with the mercapto compound of the formula III takes place, for example in the melt in an excess of mercapto compounds;

. ^ .., 109815/1963 ^ ₀ original

or preferably in aqueous, organic or organic-aqueous solution or dispersion. Suitable organic solvents are, for example, aromatic hydrocarbons such as toluene or xylenes, aromatic halogenated hydrocarbons such as chlorobenzene, aliphatic ketones such as methyl ethyl ketone or methyl isobutyl ketone, cyclic ethers such as dioxane, amides of lower fatty acids, especially dimethylformamide or dialkyl sulfoxides such as dimethyl sulfoxides. It is advisable to start from an alkali metal salt, in particular the sodium or potassium salt of the mercapto compound of the formula II, or to use alkaline agents, in the latter case especially alkali metal carbonates, such as sodium or potassium carbonate, or alkali metal hydroxides, preferably sodium or potassium hydroxide but magnesium oxide or tertiary nitrogen bases, such as pyridine, can also be used. The reaction takes place in dimethyl sulfoxide at room temperature; in all other solvents a higher temperature of, for example, 8O-14O ^C C is indicated.

If R is an alkyl or alkenyl radical, this can be straight-chain or branched; he is preferably an alkyl group of up to 12 carbon atoms. As a substituent, the alkyl radical has, for example, a Cyclohexyl, phenyl, phenylalkoxy, phenoxyalkoxy or phenoxy radical, in which the alkoxy constituent is advantageous Holds 1 to 4 carbon atoms. Preferred substituents of the Alkyl radicals R are the phenyl and the phenoxy group.

109815/1963 _ΛΰΑι

ORlQfNAL INSPECTED

The phenyl radical in the meaning of R is preferably unsubstituted. It contains, for example, fluorine, bromine or preferably chlorine as halogen atoms; as alkyl groups, preferably lower alkyl groups with up to 4 carbon atoms but also higher alkyl groups with up to 12 carbon atoms; as alkylsulfonyl groups, the methylsulfonyl or ethylsulfonyl group. As the lower alkoxycarbonyl groups of the phenyl _Ä restes R may be mentioned, for example, methoxy or ethoxycarbonyl. If the phenyl radical R contains an amino) group, this can be substituted by one or two lower alkyl groups or by one lower alkanoyl group.

If the ring A is benzofused, then the benzo radical is, for example, in the 7,8-position. Advantageous the ring A is unsubstituted or contains a methyl or ethyl group, a methoxy or ethoxy group ^ or bromine or chlorine.

As a halogen substituent, the ring B can contain, in particular, chlorine, especially in the 2-position.

However, the ring B is primarily unsubstituted.

The term "lower" before the term "alkyl", "alkoxy" or "alkancyl" means that the group or the organic Group component at most 5 carbon atoms. shows.

A second method for making the nitroacridone

dyes of the formula I consists in the fact that one

109815/1963

OftlGHNAL JNSPECTEO

Acridone compound of the formula IV,

0 SH

(IV)

in which for A and B what is stated under formula I applies, with a compound of formula V.,

Z-R (V) in the

Z denotes a substituent which can be split off as an anion and R has the meaning given under formula I.

Z in formula V is preferably halogen, such as fluorine, chlorine, bromine or iodine; but it can also be sulfated Hydroxyl group or an ester thereof, such as the methyl ester or ethyl ester or an arylsulfonyloxy group e.g. represent the phenylsulfonyloxy or ρ-methylphenylsulfonyloxy group.

Starting materials of the formula IV are obtained, for example, by reacting acridone compounds of the formula I in which X Means chlorine, fluorine or bromine, with alkali metal sulfides, such as sodium sulphide in a molar ratio of 1: 1 or with alkali metal hydrogen sulphides such as sodium hydrogen sulphide.

A mercapto compound of the formula IV is reacted with a compound of the formula V, for example by direct action of the reactants in the presence of acid-binding agents or in aqueous or in aqueous

ORIGINAL 109815/1963

organic solution or dispersion, the organic component advantageously consisting of water-miscible organic Solvents, especially lower alcohols such as methanol or ethanol, lower aliphatic ketones, preferably Acetone, cyclic ethers such as dioxane, or amides of lower fatty acids such as dimethylformamide, or lower aliphatic Sulfoxides, such as dimethyl sulfoxide, exist. As an acid-binding

A means come, for example, alkali metal carbonates or hydroxides or tertiary nitrogen bases such as pyridine; but you can do without the use of such acid-binding agents, when talking about an alkali metal salt, e.g. sodium or potassium salt of a l-mercapto-4-nitro-acridone of the formula IV goes out.

A third process for the preparation of the nitroacridone dyes of the formula I is that one is a compound of formula VI,

ft SR

^^ 1 ON- Ϊ _(vi)

NH

NO ₂

in the

one of Y ^ and Y ^ hydrogen and the other the carboxyl group or a reactive functional derivative thereof, for example a halide such as chlorine or Bromide, or an ester, e.g. a lower alkyl ester, means, under ring-closing conditions, given

1-09815 / 1963

BATH ORIGINAL

if reacted in the presence of an acidic condensing agent. Compounds of the formula VI in which Y is the carboxyl group and Y _{9 is} hydrogen are preferred for preparative reasons.

Starting materials of the formula VI, in which Y ^ is the carboxyl group and Y “represent hydrogen, for example by condensation of an optionally further substituted aminobenzenecarboxylic acid of the formula

^ _n , COOH

α If

with a benzene compound of the formula

S-R

Shark ι

NO ₂

in which Hai means chlorine or bromine, according to methods known per se [see HB Nisbet, Journal of the Chem. Soc. (London) 1933, 1372-73].

Starting materials of the formula VI in which Y «is the carboxyl group and Y, denote hydrogen, can, for example, by condensation of an optionally further substituted aromatic amine of the formula

.,H

with a 2,6-dichloro- or 2,6-dibromo-3-nitro-benzene carbon

ORiGiHAL INSPcCTSD

109815/1963

acid according to K. Lehmstedt and K. Schrader [report by German Chemical Society Volume 7t), 1526-38 (1927)] and subsequent exchange of the remaining chlorine and / or chlorine. Bromine atoms against the group -S-R produced x ^ earth.

The ring closure of the compound of the formula VI to the end product of the formula I takes place in a manner known per se and way, conveniently by heating and advantageously in the presence of an acidic condensing agent. As sour Condensing agents are preferably phosphorus oxychloride, polyphosphoric acids, and optionally also sulfuric acid Question. More information on this reaction is given in R.M. Acheson, "The Chemistry of Heterocyclic Compounds, Acridines", Pp. 105-117 (1956).

The new nitro dyes of the acridone range are suitable for dyeing hydrophobic, synthetic organic materials Fiber material, for example for dyeing textile material consisting of high molecular weight organic esters, as of cellulose di- or triacetate, but especially for dyeing textile material made from polymeric esters of aromatic polycarboxylic acids with polyhydric alcohols, especially from Polyethylene glycol terephthalate or polyclohexanedimethylol terephthalate. These dyes can also be used to dye synthetic polyamide fibers, such as polyhexamethylene adipamide, , Polycaprolactam or polyaminoundecanoic acid, as well as for dyeing polyolefins, especially polypropylene fibers be used. In addition, depending on the

109816/1963 _{ΒΑ0ΟΒΙβΙ} ΝΑ.-

Composition for dyeing or pigmenting paints, oils and waxes, as well as cellulose derivatives, in particular Cellulose esters, such as cellulose acetate, are suitable in bulk, since there are many nitroacridone dyes according to the invention are soluble in some common organic solvents, e.g. in acetone or methyl ethyl ketone.

The fiber materials mentioned are preferably colored with those according to the invention which are sparingly soluble in water Nitroacridone dyes from aqueous dispersion. It is therefore expedient to use them as disperse dyes End products of the formula I by grinding with dispersants and possibly other grinding aids to be finely divided.

Suitable anionic dispersants are, for example, the alkylarylsulfonates, the condensation products of Formaldehyde with naphthalenesulfonic acid, the ligninsulfonate; suitable non-ionic dispersants are the fatty alcohol or alkylphenol polyglycol ethers with a higher alkyl radical.

The dyeing of the polyester fibers with the dyes according to the invention, which are sparingly soluble in water, from aqueous dispersion takes place according to the processes customary for polyester materials. Polyesters of aromatic polycarboxylic acids with polyhydric alcohols are preferably dyed at temperatures above 100 ^° C. under pressure. The color can also be used in

1-09815 / 196 3 ^{BAD 0RIGfNAL}

179431?

Boiling point of the dye bath in the presence of color carriers, for example Alkalimetallphenyl-phenolates, performed Polychlorbenzolverbindungen or similar tools, or by the pad process followed by post treatment in the heat, for example, heat setting at 180-210 ⁰ C, to be made. Cellulose di-acetate fibers are preferably dyed at temperatures of 80-85 ° C., while cellulose triacetate fibers and synthetic polyamide fiber material are advantageously dyed at the boiling point of the dyebath. When dyeing the last-named types of fiber, there is no need to use color carriers. Nitroacridone dyes according to the invention can also be used for printing on the materials mentioned by customary methods.

The end products of the formula I which can be used as disperse dyes. draw on the aforementioned hydrophobic Organic fiber material, especially on PolyMthylengly- ^ colterephthalate fibers, very well and surrender! on this Fiber material strong yellow to orange colorations, which are very good light, wash, milled, rub, sweat, sublime, are solvent and decoration law. They also have, for example, dimethylformamide in organic solvents high molar absorbance. Another benefit of the new nitroacridone dyes is that they work well with combine blue anthraquinone dyes. As disperse dyes, end products are the

BATH ORIGINAL

109815/1963

Formula I preferred in which R denotes phenyl or an alkyl, alkoxy or chlorine-substituted phenyl radical. Such end products are characterized by high color strength and affinity excellent for fiber material made from polyesters, especially from polymeric esters of aromatic polycarboxylic acids with polyvalent ones Alcohols such as polyethylene glycol terephthalate fibers. In addition, the colorations produced with them are very fast on this type of fiber, in particular light, rubbing, subliming and washable.

But are also very valuable p \ vh such water-insoluble end products of formula I, wherein R is an alkyl group, as they acid- well and are resistant to alkali.

Dyes of the formula I according to the invention which containing basic-making groups are, as salts of a strong inorganic or organic acid, usually in Well soluble in water. They draw from aqueous, neutral or - advantageously - from weakly acidic liquor, if necessary in the presence of wetting agents, such as addition products of alkylene oxides with higher alcohols, on fiber material made of polymeric or copolymeric acrylonitrile when heated in an open or in a closed vessel under pressure and result in real, in particular wash-, decatur- and lightfast yellow to orange colorations on this material.

In the following examples the temperatures are given in degrees Celsius. The melting points given are uncorrected.

1-098 15/1963

EXAMPLE 1

In a: dispersion of 41.2 g of finely powdered l-chloro - ^ - nitro-acridon (Srap. 250 - 251 °) and 24.9 g 4-chlorothiophenol in 300 ml of dimethyl sulfoxide verden at Room temperature (20 °) with good stirring 12 g of anhydrous Potassium carbonate entered. The temperature rises to 45 °. After a short time. The yellow pulp that has developed over time slowly heated to 90-95 ° and stirred at this temperature for 1 hour. The mixture is then cooled to 50 ° and 1500 ml of Yasser are added. The precipitated yellow reaction product is stirred for a further 20 minutes and then filtered off. It is washed with hot water and then dried. The yield is 57.4 g.

The obtained nitro dye of the above formula colors after grinding with the sodium salt of the condensation products naphthalene-2-sulfonic acid with formaldehyde in the presence of sodium o-phenylphenolate as swelling agent, .... Polyethylene glycol terephthalate fibers in greenish-yellow, very good wash, rub, light and sublimation fast dyeing

109815/4963

- IJ -

If the procedure is otherwise identical, instead of 41.2 g of l-chloro-4-nitro-acridone, 47.9 g of l-bromo-4-nitroacridone are used (Mp. 252-254 °) [obtained by condensation of 1-nitro-2,4-di-bromobenzene with the potassium salt of 2-aminobenzene-1-carboxylic acid and ring closure of the 2-nitro-5-bromo-diphenylamine-2'-carboxylic acid formed of melting point 240 ° -242 ° in sulfuric acid], the nitroacridone dye is likewise obtained of the formula above.

Is used instead of the 24.9 g of 4-chloro-thiophenol the equimolar amount of one of the following Table I, Column 2, listed mercapto compounds and sets them according to the above with 4.1.2 g of 1-chloro-4-nitro-acridone or with 47.9 g of l-bromo-4-nitro-acridone, end products are obtained which contain polyethylene glycol terephthalate fibers the real shades listed in column 3 of this table.

109815/1963

TABLE I.

2 3 4 5 6 7 8 9 10 11 12 13

16

17 18 19 20 21 22

23

Mercapio connection

HS

HS

HS

HS

HS

HS

HS

HS

HS

HS

HS

HS

HS

HS

HS

HS HS HS HS HS HS -

C ₂ H ₅ C ₃ H ₇

" ^C 12 ^H 25

- CH ₂ -CH ₂ -OH

- CH ₂ -CH ₂ -OCH ₃ '·

- CH ₂ -CH ₂ -OC ₂ H ₅ '

- CH ₂ -CH ₂ -CH ₂ -OCH ₃

- CH ₂ -CH ₂ -CH ₂ -OC ₂ H ₅ CH ₂ -CH ₂ - 0- ~ CH ₂ -CH ₂ -COC ₂ H ₅ CH ₂ -COOCH ₃ CH ₂ -COOC ₂ H ₅ CH ₂ -COO- ISO-C ₈ H ₁₇

CH ₂ -COO-CH- (CII ₂ ) ₃ -CH ₃ C ₂ H ₅

CH ₂ -COO-ZJi)

CH ₂ -COO-Ch ₂ -CH ₂ -OCH ₃

CH ₉ -COO-CH ₂ -CH ₂ -Ch ₂ -OCH ₃

CH ₂ -CH ₂ -NH ₂

CK ₀ -CH ₀ -NII-CIU

CH _n -CH ₀ -N. ^J ^ ^X CH shade on polyethylene glycol terephthalate fibers

HS - CII ₀ -CH ₂ -NC ₂ H

greenish yellow

yellow

greenish yellow η

yellow

6/1963 INSPECTED

TABBLLS I (continued)

Merc & ptoverbin & ung Shade au? Poly & t / .yler.-glycol terephthalate teaser

HS KS - CH,

'.-O ⁰¹

Cl

Cl

HS - CH

HS - HS - CH ₂ -.

HS - CH ₀ - <f> OCH

HS - CIL HS -

Br

HS -0

Cl

Cl, Cl

HS

V ^cl

HS - /> - i; o ₂ yellow

reddish yellow

-J

BATH ORIGINAL

10981S / 1 963

TABKLLE I (Forisotzung) - 16 -

No.

35

36

37

38

39

41

42

43

44

45 46

. 47

48.

Kev cap tover bind un

OCH.

Cl

Cl CF.

KS

cn.

^CK

KS - //

on ft -

KS ~ \ _

^ ₃

^CK 3

P IT

^U S * '19

f'25

"'3

CCCCH ₃ shade on Polyäthylei glycolterephrhala ^ fase:

reddish - yellow

yellow

greenish - yellow

yellow

reddish yellow

greenish yellow

109815/1963

TABLE I (? Supposition)

IiCr.

Hue on

49 50 51

52 53 54

55 56

57 58

HS

HS

HS

COOC ₂ K ₅

CONH ₂

CONHCIL

CON

HS JS

HS

KS

HS

HS -

CH.

OCI

HS

HS

- / "V-KH

HCOCH-

59 HS

greenish yellow

yellow

109815/1963

BAD ORrGlNAl ₄ EXAMPLE '60

40 g of thiophenol are mixed with 4 g of a SOpigen aqueous Potassium hydroxide solution heated to 60 °. One carries into the solution with stirring 8.24 g of 1-chloro-4-nitro-acridone and heated then the mixture for another 10 minutes at 110 - 115 °. After the Cooling to 100 ° vird the yellow suspension in a 60 ° varr.e Stir in a solution of 16 g of sodium hydroxide in 500 ml of water. The precipitated yellow nitro dye of the formula above is stirred for a further 20 minutes at 60 ° - 70 ° and then filtered off, it is washed free of alkali with hot water and then dried. The yield is 11 g.

The dye obtained in this example dyes after grinding with the sodium salt of a condensation product the naphthalene-2-sulfonic acid with formaldehyde in the presence of Sodium o-phenylphonolate, polyethylene glycol tercphthalate fibers .in very good vaach, rubbing, light and sublimation fast pungent golbon hues.

109815/1963

BATH ORIGINAL EXAMPLE 61

H ₃ C

O S—

KO ₂ ■ ■

6.1 g of 1-chloro-4-nitro-7-methoxy-acridone (prepared by condensation of 4-methoxy-aniline with 2,6-dichloro-3-nitrobenzene-1-carboxylic acid and subsequent ring closure by methods known per se; Srnp. 261 - 262 °) are nit 3.64 g of 4-isopropyl thiopheriol and 2 g of anhydrous potassium carbonate in 150 μl of methyl isobutyl ketone under reflux for 4 hours • .heated. Then the methyl isobutyl ketone with Vasserdanvpf ■. Distilled off and the precipitated orange-red product filtered off, washed with hot yasser and then rocked. The yield is 8.5 g

This dye dyes polyethylene glycol terephthalate fibers in an aqueous dispersion in the presence of sodium o-phenylphenolate with very good wash, rub, light and sublime properties reddish-yellow hues.

Also reddish yellow dyes of similar good quality

•• coloring properties are obtained when ir.an at the same procedure, the 6.1 g of 1-chloro-4-nitro-7 -.-. ethoxyacridone by 6.4 g of l-chloro-4-nitro-7-ethoxy-acridone (m.p. 241- • 243 °) ι or 6.4 g of l-chloro ^ -nitro ^ -methylmercapto-acridone (Snip. 256 - 258 °), or? - '* 2 g l-chloro ~ 4-nitro-7-? Heno>: yacridone (Srcp. 218 - 219 °) replaced.

109815/1963

EXAMPLE

6.1 g of 1-chloro-4-nitro-6 ~ n2ethoxy-acridcn (prepared by condensation of 3-methoxy-aniline with 2,6-dichloro-3-nitrobenzene-1-carboxylic acid and ring closure in phosphorus oxychloride; M.p. 251-252 °) with 2.54 g of thiophene-nol and 2 g of anhydrous potassium carbonate in 100 ml of dimethyl sulfoxide Heated to 90-95 ° for 30 minutes. After cooling to room temperature 500 ml of water are added to the dispersion and the yellow reaction product which has precipitated is filtered off. It is washed with hot water and dried. The yield is 7.5 g of nitro dye.

Replaces the l-chloro-4-ni'tro-6-methoxy-acridone by the same amount of l-chloro-4-nitro-5-methoxy-acridone (produced by the condensation of 2-methoxy-aniline with 2, o-dichloro-S-nitro-benzene-l-carboxylic acid and then • ring closure according to the usual methods; M.p. 316-318 °) and • otherwise proceeds as indicated in this example, then maxi also receives a yellow nitrate dye.

109815/1983

2 parts by weight of the dyes thus obtained are brought into a finely dispersible form by grinding with 6 parts by weight of a lignosulfonate. Using these dye preparations, polyglycol terephthalate fibers are dyed in an aqueous dispersion in the presence of sodium o-phenylphenolate in yellow shades. The colors are very light, wash, rub and sublime fast. Example 63

0 S- (CH ₂ ) J ^ ₁ -CH ₃

2
In a suspension of 5.8 g of l-chloro-A-nitro-7-methyl-

acridon in a solution of 4.44 g of n-dodecyl mercaptan and 90 ml Dimethylformamide are added 2 g of anhydrous potassium carbonate at room temperature with stirring. After that, the Suspension heated to 110 ° for 1 1/2 hours. After cooling to room temperature, the reaction mixture is diluted with 500 ml of water, the suspension is stirred for a further 20 minutes and then the orange-yellow reaction product obtained is filtered away. It is washed with water and dried. The yield is 9 g of the nitroacridone dye from the above Formula. 1-chloro-4-nitro-7-methylacridone can be prepared in the following way: 12.1 g of 5-methyl-2-aminobenzene-1-carboxylic acid are heated to 70 - 80 ° with 325 ml of amyl alcohol. At this temperature, 12.1 g of water

INSPECTED

109815/1963

free potassium carbonate entered. It is then heated to the boil and 50 ml of amyl alcohol is distilled off. After cooling to 60 °, 17.8 g of 2-dinitro-4-chlorobenzene are added and the mixture is heated to the boil again. There arises thereby a red solution, from which the red potassium salt of 2-nitro-5-chloro-diphenylamine-4'-methyl-2 fails ^1-carboxylic acid. The easily stirrable, red suspension is kept at the boil overnight. It is then cooled to room temperature and the precipitated potassium salt is filtered off. It is slurried with 300 ml of water and acidified with 40 ml of 15% hydrochloric acid. After adding 6 g of sulfamic acid, the still adhering amyl alcohol is distilled off with steam. The yellow product is filtered off while still hot, washed with water and dried. Yield: 22.3 g. M.p. 240-241 ° (from glacial acetic acid). The ring closure to the l-chloro-4-nitro-7-methyl-acridone is carried out in the usual way in polyphosphoric acid. M.p. 238-240 °.

Is used in Example 63 instead of 5.8 g of 1-chloro-4-nitro-7-methyl-acridone 6.1 g of l-chloro-4-nitro-7-ethyl-acridone (melting point 222-224 °) or 6.33 g of l-chloro-4-nitro-7-isopropyl acridone (M.p. 261-263 °) and if the rest of the procedure is as indicated in the above example, orange-yellow dyes are also obtained.

These dyes dye polyethylene glycol terephthalate fibers in aqueous dispersion in the presence of sodium o-phenylphenolate in very light-, wash-, rub- and sublime-fast reddish-yellow shades.

109815/1963 orighnal inspected

At ST) iel 64

5.8 g of 1-chloro-4-nitro-6-methyl-acridone (produced by condensation of 2-broni-4-chloro-1-nitro-benzene with the potassium salt of 4-methyl-2-aminobenzene-1-carboxylic acid and subsequent ring closure in polyphosphoric acids (No. 283-284 °) are heated to 90-95 ° for 30 minutes with 2.42 g of thiophenol, 1.8 g of anhydrous potassium carbonate and 90 ml of dimethyl sulfoxide. After cooling to room temperature, the yellow suspension is stirred into 500 ml of water. The precipitated yellow dye is filtered off, washed with water and dried. The yield is 7.5 g of xitroacridone dye of the formula above. Replaces the 5.8 g of 1-chloro-4-nitro-6-iT.ethylacridone with 5.8 g of l-chloro-4-nitro-8-methylacridone (produced by the condensation of 2-Bro _i Ti-4-chlorine -l-nitro- enxol with the potassium salt of 6-methyl-2-a.iiinobenzene-1-carboxylic acid and subsequent ring closure in polyphosphoric acid; S.irp. 216 °), then with otherwise the same procedure, a yellow one is also obtained Dye.

109815/1963

6.48 g of l-chloro-4-nitro-7,8-benzacridone (produced by condensation of 2-xaphthylamine with 2,6-dichloro-3-nitrobenzene-l-carboxylic acid and ring closure in phosphorus oxychloride; ( S.-rp y 330 °) are heated with 2.64 g of thiophenol, 1.7 g of anhydrous potassium carbonate and 150 ml of dimethyl sulfoxide for 1 hour to 90-95 °. After cooling, the yellow suspension is stirred into 500 ml of water and the mixture The mixture is stirred for a further 10 minutes. The precipitated yellow dye is filtered off, washed with hot vassar and then dried. The yield is 7.8 g of xitroacridone dye of the formula above. The 6.48 g of 1-chloro-4-nitro is replaced -7,8-bonzacridone by 6.48 g of l-chloro-4-nitro-6,7-benzacridone (produced by the condensation of l-nitro-2-bromo-4-chlorobenzene with the potassium salt of 2-naphthylamine -3-carboxylic acid and subsequent ring closure in phosphorus oxychloride, brown-red crystals from o-dichlorobenzene, melting point 333-335 °, decomposition), or by 7.0 g of l-chloro-4-nitro-7-phenylacr idon (Smp. 258-260 °), then with otherwise the same procedure, yellow ear substances are also obtained.

These dyes color after grinding with the sodium salt of the condensation products of naphthalene-2-sulfonic acid and form: aldehyde in the presence of sodium-o-phenylphonolate Polyäthylon ^ lykolterephthalatfäuren with very good light, wash, rub and sublime rights yellow tones.

BAD ORtQUNAL

109815/1963

EXAMPLE 66

O S

₂
6.2 g of 1,2-dichloro-4-nitro-acridone (manufactured by

Condensation of l-xitro-2,4,5-trichlorobenzene with the potassium salt of 2-az3inc-benzene-l-carboxylic acid and subsequent ring closure in phosphorus oxychloride. (Snip 220 -. 221 °) Verden with 3.2 g of potassium thicphenolat and 200 ml of o-xylene is heated for 5 hours at 135 °. The o-xylene is then distilled off with steam, the orange-red product which has precipitated is filtered off, washed with hot l'assex and dried. The yield is 7.6 g of the nitro dye of the formula above.

5 parts by weight of this dye account for 15 parts by weight Grind the sodium salt of the condensation products of naphthalene-2-sulfonic acid and formaldehyde. This Dye preparation dyes in an aqueous dispersion in the presence of sodium o-phenylphenolate polyethylene glycol / terephthalate fibers in reddish-yellow hues.

109815/1963

^ßAD original

Example 67

Replaces the 6.2 g of 1,2-dichloro - ^ - nitroacridone in Example 66 with 6.9 g of 1,2,6-trichloro-4-nitro-acridone (produced by condensation of 2, A _} 5-trichloro l-nitrobenzene with the potassium salt of 2-amino-4-chlorobenzene -! - carboxylic acid and subsequent ring closure in phosphorus oxychloride, yellow-brown crystals from 1,2-dichlorobenzene, melting point 2S7-2SS ⁰ ), then obtained at otherwise the same procedure, also a reddish-yellow dye.

109816/1963 _{BAD 0R1QIHAL}

179h317

See 68

7jl g of l-Brcrr .- ^ - nitro-ö-chloro-acricGn (produced by the condensation of l-Kitro-2, S-dibrcmbenzene with the potassium salt of <-Chlor-2-air.inc-benzene-l-carboxylic acid and subsequent addition in phosphorus oxychloride, Snip. 29C-2S2 ⁰ ) or 6.2 g 1,6-dichloro- <-nitro-acridone (produced by condensation of 1-nitro-2-brciTi-4-chlorobenzene with the: Kaliur .salt of 4-chloro-2-arr.inobenzene-1-carboxylic acid and ring closure in phosphorus oxychloride; Sn-p. 257-258 °) in 12C ml of dimethyl sulfoxide advises 2.64 g of thiophenol and 2 g of anhydrous potassium carbonate 30 KinuLen to 90 - 95 ° heated. After adding 5CC ml of water, the whole thing is cooled to room temperature; the precipitated yellow React Lions product is filtered off with; V / ater washed and then dried. The yield is 7.5 g of the yellow xitrile dye of the formula above.

BATH ORIGINAL

1 0981S / 1 963

Example 69

In Example 68, the 6.18 g of 1,6-dichloro-4-nitrcacridone are replaced by 6.13 g of 1,7 ~ dichloro-4-nitro- & cridon (manufactured by Condensation of l-nitro-2-bromo-4-chlorobenzene with the potassium salt of 5-chloro-2-aminobenzene-1-carboxylic acid and ring closure in phosphorus oxychloride, orange-red crystals from 1,2-dichlorobenzene, M.p. 300 - 301 °), then one obtains, with otherwise the same working method, also a yellow nitro color of the above, Formula.

109815/1963

SAD

EXAMPLE 70

• NO

6.4 g of 1-chloro-4,7-dinitfo-acriaon [manufactured by K. Lehmstedt and E. Schrader B.70, 1526 - 1538 (1937) in 150 al of dimethyl sulfoxide with 4 g of 4-tert-butylthiophene / and 2 g v / aterfr & ieni sodium carbonate 40 minutes at 90 - 95 ° / 'heated. After cooling, the suspension is 500 ml passer diluted} the resulting yellow product is filtered off, washed with water and dried at 80-90 °.

. The yield is 8.8 g of the nitro dye of the formula above. . '

The dye colors after grinding rait the Natriu ^ - salt of the condensation products of>^"T aphtalin-2-sulfonic acid with formaldehyde in the presence of a Quellraittels, Polyglyliolterephthalatfasern in greenish-yellow shades. The coloring • is very good light, wash, rubbing and sublining fast.

BATH ORIGINAL

109815/1963

EXAMPLE 71

NH,

5.8 g of 1-chloro-4 ~ niiro-7-amino- & criaon (manufactured by condensation of 4-acetylamino-aniline with 2,6-diehlor-3-nitro-benzene ~ 1-carboxylic acid and ring closure with simultaneous hydrolysis of the acetylamino group in Schvefel acid; brownish-violet crystals from o-dichlorobenzene, Mp 300 °) are suspended at room temperature in 120 μl of dimethyl sulfoxide and 2.64 g of thiophenol and added with 2 g anhydrous sodium carbonate is added. After that, the The suspension is slowly heated to 90-95 ° and stirred for a further hour at this temperature. After cooling to room temperature the suspension is stirred into 500 ml of water, the dye completely precipitating. The brownish violet ;: The reaction product of the above formula is filtered off ur.cL washed with water. It is dried at 70-80 ° in a vacuum. The yield is 7.2 g.

This dye stains in the presence of an aqueous dispersion of Netrium-o-phenylphenolate, polythylene glycol terophthalate fibers in brown-red shades.

7.26 g of this dye were treated with 80 nil glacial acetic acid and * d 30 ml acetic anhydride heated to boiling for 2 hours.

109815/1963

BATH

The got l-? Hon
crystallizes in red crystals on cooling. These are filtered off and washed with alcohol, then with Vasser and dried. .

This dye dyes polyethylene glycol terephthalate fibers in aqueous dispersion with the presence of swelling agents in orange-red shades. The colorations are very fast to wash, rub, light and sublime.

BATH

109815/1963

EXAMPLE 72

5 »5 g of l-chloro-4-nitro-acridone are at room temperature and while stirring in a solution of 1.8 g of sodium sulfide in 120 El Aethenol and 30 ml Vasser entered. Measure increased the reaction mixture keeps this at 60-70% with stirring Temperature for 10 minutes and add to this mixture then 5 g of benzyl chloride. After four hours of boiling under The device is allowed to cool under reflux and the filter is filtered

• precipitated crude benzylthio-4-nitro-acridone of the above Formula off. Kach cleaning by un & ristailizing from chlorobenzene, the reaction product is identical to that ;. Dye prepared according to Example 25.

Use raan in this example, otherwise the same

• ^ by the way, instead of the 5 g of benzyl chloride, the equimolarc amount one of the compounds listed in Table II below, column 2, this gives dyes, velche '• Polyethylene glycol terephthalate fibers in the column 3 the real shades given in this table.

109815/1963

BATH ORIGINAL

TABLE II

Example no.

Verbir. & Un «? Shade on poly ^ lyholterepb / thclatf aserav.

73

74 75

76

77 78 79 80 81 82 83

Br - CH

2 Λ \

^C1 - ^CH 2 -i J- ^Q1

Cl - CH ₂ - /)> - Cl • Cl

Cl - CH ₂ -

Br - CH ₂ - · CH ₂ - / J - C ₂ H ₅

Br- (CH ₂ ) ₄ - CH ₃ Br - CH ₀ - CH = CH

Br - CH ₂ - CH = CII - CH ₃

Cl - CH ₂ - CO - CH ₃

Cl - CH ₂ - CH ₂ - OC ₂ H ₅

Cl - CH ₂ - OC ₂ II ₅

Cl - CH ₂ - CII ₂ - OH

Br - CII ₂ - CH ₂ - 0 - Q

greenish yellow

yellow

109815/1963 ORfGINAl

TABLE II (continued)

Ex. Xr.

Connection Br - CS -Q

CH ₃

C ₂ HO - SO ₂ - OC ₂ H ₅

Cl

NO ₀ "V ₄

-SO ₉ CH-

p - f ~ \ -COOCII

• ^N0 color on polyglycol-i terephthalate fiber

yellow

reddish yellow

reddish yellow

golb

109815/1863

BATH ORIGINAL

1794

Example 93

O S-CH _o CH _o CH _o - (. CH ₃ , Ii Γ 2 2 2 W

In a suspension of 14.43 g of 1-chloro-4-nitro-7-methylacridone, 8.4 g of 7-phenylpropyl mercaptan and 180 ml of dimethylformamide 9.61 g of a 30.97cigen sodium methylate solution are introduced with cooling with water Suspension heated to 65-70 ° and stirred for 1 hour. The reaction mixture is then allowed to work for a further 20 minutes Heated to 90 ° and then cooled to 10 °. The precipitated reddish-yellow nitro dye of the above formula is filtered off, washed with methanol and water and dried. The yield is 17.8 g.

The nitro dye obtained stains after grinding with the sodium salt of the condensation product of naphthalene-2-sulfonic acid with formaldehyde from an aqueous dispersion in the presence of sodium o-phenylphenolate, polyethylene glycol terephthalate fibers in reddish-yellow tones. The colors are very wash, rub, light and sublime fast. This dye also has a particularly good wool reserve.

If you use 14.43 g of l-chlorine ^ -nitro -? - Methyl acridone, 13.74 g of 1-chloro-4-nitroacridone or 15.94 g l-chloro-4-nitro-7-ethoxyacridone and proceeds as otherwise

109815/1963

I / J ¹ Tv) I /

given in the above example, 16.2 g of des are obtained yellow l - ^ - phenylpropylmercapto - ^ - nitroacridone dye or 20.2 g of the corresponding red-orange 7-ethoxyacridone

dye.

ORJCWNAL INSPECTEC

109815/1963

1734317

Example 94 O S-CH ₂ CH ₂ OCH ₂ -Q

In a suspension of 15.45 g of l, 6-dichloro-4-nitroacridone, 9.25 g, β-benzyloxyethyl mercaptan and 170 ml of dimethylformamide 9.85 g of a 30.2% sodium methylate solution are entered at 20-25 °. After that the suspension heated to 70 ° for 1 hour and then to 90 ° for 10 minutes. The reaction mixture is then cooled. The precipitated yellow product is filtered off, washed with ethanol and water and dried. The yield is 17.8 g.

The obtained nitro dye of the above formula colors after grinding with the sodium salt of the condensation product of naphthalene-2-sulfonic acid with formaldehyde in the presence of sodium o-phenylphenolate polyethylene glycol terephthalate fibers in greenish yellow tones. The colors are very lightfast and sublimation fast.

Instead of 15.45 g of 1,6-dichloro-4-nitroacridone, 13.74 g of l-chloro-4-nitroacridone are used and the procedure is followed otherwise as indicated in the above example, the corresponding 4-nitroacridone dye is obtained.

109816/1963

Example 95

In a suspension of 11.55 g of 1-chloro-4-nitro-7-methylacridone, 6.96 g of cyclohexylpropyl mercaptan and 170 ml of dimethylformamide are added with stirring for 30 minutes Entered 7.86 g of a 30.2% strength sodium methylate solution. The suspension is then stirred for a further 20 minutes at 25-30 ° and then heated to 70-75 ° for 1 1/2 hours. After cooling to 10 °, the precipitated reddish yellow product is filtered off, washed with ethanol and water and dried. The yield is 15.2 g.

The resulting nitro dye of the above formula colors after grinding with the sodium salt of the condensation product of naphthalene-2-sulfonic acid with formaldehyde in the presence of sodium o-phenylphenolate polyethylene glycol terephthalate fibers in reddish-yellow tones. The colors are very lightfast and sublimation fast.

109815/1963

I / J 'i O ι /

Example 96

O S- (CH ₂ ) J- /

In a suspension of 12.2 g of 1-chloro-4-nitro-5-methoxyacridone, 7.92 g of ^ -phenylamyl mercaptan and 150 ml of dimethylformamide are 7.95 g with cooling and stirring registered a 30.2% sodium methylate solution. Thereafter the suspension is heated to 70 ° and stirred for 2 hours at this temperature. After cooling the reaction mixture the precipitated nitro dye of the above formula is filtered off to 10 °, with methanol and Water washed and dried. The yield is 16.9 g.

The nitro dye obtained stains - after grinding with the sodium salt of the condensation product of naphthalene-2-sulfenic acid with formaldehyde - in the presence of sodium o-phenylphenolate polyethylene glycol terephthalate fibers in reddish-yellow tones. The colors are very lightfast and sublimation fast.

If equivalent amounts of Q- phenylbutyl mercaptan or ß-phenylethyl mercaptan are used instead of ε-phenylamyl mercaptan and the procedure is otherwise as indicated in the above example, the corresponding 4-nitroacridone dyes falling under formula I are obtained, which also give colorations with good properties on polyethylene glycol terephthalate fibers .

10 9815/1963

1704317

Example 97

9.85 g of a 30.2% sodium methylate solution are introduced into a suspension of 13.74 g of 1-chloro-4-nitroacridone and 10.6 g of Q- phenoxybutyl mercaptan in 170 ml of dimethylformamide, while cooling with ice water and stirring. The suspension is then heated to 70-75 ° and stirred at this temperature for 2 hours. After cooling down de? In the reaction mixture to 10-15 °, the precipitated yellow nitro dye of the above formula is filtered off, washed with ethanol and water and dried. The yield is 19.1 g.

Is used instead of 10 g £) -Phenoxybutylmercaptan 9.25 g of 7-phenoxypropyl mercaptan and if the procedure is generally as indicated in the above example, a further one is obtained yellow nitroacridone dye.

Both dyes dye polyethylene glycol terephthalate fibers in an aqueous dispersion in the presence of sodium o-phenylphenolate in very light, wash, rub and sublime-fast yellow tones.

OFHQHNAL INSPECTED

1 09815/1963

Example 98

In a suspension of 13.73 g of 1-chloro-4-nitroacridone and 10.9 g of ß-mercapto-ß-phenoxy diethyl ether in 170 ml of dimethylformamide 9.83 g of a 30.2% strength sodium methylate solution are added with stirring over a period of 30 minutes. The reaction mixture is then cooled to 10-15 °. The precipitated yellow nitro dye of the above formula becomes filtered off, washed with methanol and water and dried. The yield is 19.3 g.

The nitro dye obtained stains - after grinding with the sodium salt of the condensation product of maphthalene-2-sulfonic acid with formaldehyde from an aqueous dispersion in the presence of sodium o-phenylphenolate polyethylene glycol terephthalate fibers in yellow tones. The colors are very lightfast and sublimation fast. This dye has also has a very good reserve of wool.

ORIGINAL INSPECTED

109815/1963

copy

EXAMPLE 99 ■

24.9 g of 2-nitro-5-n-butylmercaptodiphenylamine-2'-carboxylic acid (produced by condensation of 3-chloro-4-nitro-in-butylmercaptobenzene with 2-aminobenzene-1-carboxylic acid in the presence of potassium carbonate, according to HH Hodgson and FW Handley, J. Chem. Soc. 1928 , 166) are heated to boiling with 110 g of phosphorus oxychloride with thorough stirring within 20 minutes and then kept at the boil for a further 30 minutes. After cooling to room temperature, the excess phosphorus oxychloride is decomposed with 1000 g of ice water. The resulting dispersion is heated to 90-95 ° for 45 minutes and the precipitated product is filtered off while hot, washed with hot water and then dried. The yield is 18.5 g of the nitro dye of the formula given above.

The dye obtained in this example colors after grinding with the sodium salt of a condensation product of naphthalene-2-sulfonic acid with formaldehyde in Presence of sodium o-phenylphenolate, polyethylene glycol terephthalate fibers in greenish yellow tones.

109815/196 3 owohal

Example 100

24.9 g of 2-nitro-5-n-butylmercaptodiphenylamino-6-carboxylic acid (produced by condensation of 2-nitro-5-chloro-diphenylamine-6-carboxylic acid with n-butyl mercaptan in the presence of potassium carbonate) are concentrated in 210 g Sulfuric acid added and heated to 90-95 ° for 2 hours with stirring. After cooling down the resulting solution is added dropwise to 1500 g of ice water. The yellow product obtained is filtered off and washed acid-free. To clean it, it is suspended in 500 ml of water, mixed with 5 g of sodium carbonate and then heated to 50 ° for 45 minutes. The dye is then filtered off, washed with water and dried. The yield is 17.8 g.

The dye obtained is identical to the example wet 99 manufactured-product identical.

JNSPECTEO

109815/1963

Dyeing prescriptions:

a) 2g of the dye obtained according to Example 60 are dispersed in 4000 g of water. 12 g of the sodium salt of p-phenylphenol are added to this dispersion as a swelling agent as well as 12 g of diammonium sulfate and dyes 100 g of yarn made of polyethylene glycol terephthalate 1 1/2 hours at 95-98 °. The dye is rinsed with water and then with post-treated dilute aqueous sodium hydroxide solution and a dispersant. This gives you a right to wash, light and sublime greenish yellow color.

In this example, 100 g of polyethylene glycol terephthalate yarn are replaced through 100 g cellulose triacetate fabric, dyed under the specified conditions and then rinsed with water, a greenish-yellow coloration that is very washable and sublime-fast is also obtained.

ORlGHNAL INSPECTED

109815/1963

b) 2 g of the dye obtained according to Example 63 in 2000 g of water, the 4 g Contains oleyl polyglycol ether, finely dispersed. The pH of the dyebath is adjusted to 6-6.5 with acetic acid.

You now go with 100 g of fabric made of polyethylene glycol terephthalate at 50 °, the bath is heated to 130 ° within 30 minutes and dyes the fabric for 50 minutes Temperature. The dye is then rinsed with water, soaped and dried. One receives in compliance under these conditions a reddish yellow coloration that is washable, sweaty, lightfast and sublimated.

The dyes described in the other examples also produce colorations that are more evenly matched by this process Quality.

ORIGINAL WSPECTED

109815/1963

c) Polyethylene glycol terephthalate fabric is impregnated on a padder at 40 ° with a liquor of the following composition:
20 g of the dye according to Example 1 finely dispersed in:

7.5 g sodium alginate
20 g triethanolamine

20 g octylphenol polyglycol ether and g water.

The fabric, which has been squeezed off to a content of approximately 100% (based on the dry weight), is dried at 100 ° and then fixed for 30 seconds at a temperature of 210 °. The dyed goods are made with Rinsed with water, soaped and dried. Under these conditions, one obtains a fastness to washing, rubbing, light and sublimation greenish yellow color.

OWGrtNAL

109815/1963

d) 0.5 g of the obtained according to Example 22 basic dye are made into a paste with 0.5 g 807 _o acetic acid and dissolved by adding 4000 g of hot water. Another 1 g of 80% acetic acid, 2 g of sodium acetate and 4 g of an adduct of 15 mol of ethylene oxide with oleic alcohol are added to this solution, and 100 g of polyacrylonitrile fibers are added to this bath. The bath is heated to 90 ° within 30 minutes, kept at this temperature for 10 minutes and the fibers are then dyed at the boil for one hour. The dyebath is almost completely exhausted. The dyed material treated in this way is then soaped for 15 minutes at 80 ° in 5000 g of water with the addition of 6 g of the sodium salt of oleic acid-N-methyl-N-sulfonic acid-ethylamide, then rinsed and dried. The polyacrylonitrile fibers are dyed in pure yellow shades with excellent washing and decorative fastness properties.

103815/1963

e) 0.8 g of the, according to the example. 44 obtained, finely dispersed Dye are added to 2500 g of water containing 1.5 g of oleyl polyglycol ether and 1.5 g of ammonium sulfate. Man goes into the dye bath with 100 g of polypropylene yarn at 50 °, heats to 100 ° within 30 minutes and dyes for one Hour at this temperature. The yarn is then rinsed with hot water and dried. A strong color is obtained yellow coloring of very good lightfastness and good fastness to washing and exhaust gas.

ORIGINAL INSPECTED

109815/1963

Claims (1)

Claims 1. Nitroacridone dyes of the formula I. S-R (D in the R is an alkyl containing not more than 18 carbon atoms or alkenyl radical; an alkyl radical containing not more than 12 carbon atoms, by a hydroxyl, lower alkoxy, phenylalkoxy, phenoxy-alkoxy, phenoxy, cyclohexyl, phenyl, lower Alkoxycarbony1-, Cyclohexyloxycarbonyl-, Alkoxyalkoxycarbonyl-, lower alkanoyl, or optionally by a lower alkyl, a cycloalkyl or a Benzyl group substituted amino group; a cyclohexyl radical; a benzyl group substituted by a methyl or methoxy group or halogen; a phenyl radical, which is optionally replaced by at least one of the following substituents: halogen, trifluoromethyl, nitro, Cyano, alkyl, lower alkoxy, lower alkylsulfonyl, lower alkoxycarbonyl, carbamoyl, lower alkylcarbamoyl, Di-lower alkyicarbamoyl or an amino group optionally substituted by a lower alkyl or alkanoyl group 109815/1963 SQ 179 ^ 317 is substituted; or denotes a naphthyl radical, and in which the ring A is unsubstituted or a lower alkyl or lower alkoxy group, has a nitro group, an amino group or halogen or is condensed with a benzene nucleus and the Ring B is not further substituted or is substituted by a halogen. 2. Nitroacridone dyes of the formula I according to claim 1, in which R is the phenyl radical or an alkyl group through chlorine or a lower alkoxy group-substituted phenyl radical .beletes. 3. Nitroacridone dyes of the formula I according to claim 1, in which R is an alkyl radical having up to 12 carbon atoms. 4. nitroacridone dyes of the formula I according to claim 1, wherein R is an alkyl radical which is replaced by a phenyl or phenoxy radical is substituted. March 10, 1970 10 9 8 15/1963 OW ^ nal inspected