US4764175 provides monoazo and disazo compounds having a 1-hydroxy-5, 6-, 7-or 8-substituted 1,3,5-triazinylamino-3- or 4 sulfonic acid coupling component radical.

However there is still a need to produce dyes having improved properties. Surprisingly, it was found that dyes according to formula (I) as shown below of the present application have those desired properties.

According to the invention there are provided compounds of formula (I) wherein R, is H; C1-C4alkyl or C,-C4alkyl monosubstituted by-OH, X, and X2 independently of each other are an aliphatic, cycloaliphatic, aromatic or heterocyclic amino group, and at least one amino group comprises a protonatable nitrogen atom or a quaternary ammonium group, and being an aliphatic, cycloaliphatic, aromatic or heterocyclic mono (C, 4alkyl)-amino group, the C, 4alkyl-group being unsubstituted or monosubstituted by halogen, C, 4alkoxy, C, 4alkyl, phenyl or hydroxy; an aliphatic, cycloaliphatic, aromatic or heterocyclic di (C1-4aikyl)-amino group, the Ci-

4alkyl-groups being independently unsubstituted or monosubstituted by halogen, C1-4alkyl, C1-4alkoxy, phenyl or hydroxy; a C5-6cycloalkylamino group, the cycloalkyl group being unsubstituted or substituted by one or two C1-2alkyl groups; a phenylamino group, the phenyl ring being unsubstituted or substituted by one or two groups selected from halogen, C, 4alkyl, C, 4alkoxy, hydroxy and phenoxy; or a 5-or 6-membered ring containing one or two hetero atoms, in addition to N, O or S, which heterocyclic ring is unsubstituted or substituted by one or two C1-4alkyl groups; or a group Z, where Z is independently selected from

p is 0 or an integer 1,2 or 3, each R2 is independently H; unsubstituted C, 4alkyl or C, 4alkyl monosubstituted by hydroxy, halogen, cyano or C1-4alkoxy, each R3 and R4 is independently H; unsubstituted C,. 6alkyl ; C2. 6alkyl monosubstituted by hydroxy or cyano; phenyl or phenyl-C, 4alkyl, where the phenyl ring of the latter two groups is unsubstituted or substituted by one to three groups selected from chlorine, C1-4alkyl, C1-4alkoxy, unsubstituted C5-6cycloalkyl or C5-6cycloalkyl substituted by one to three C1-4alkyl groups, or a pyridinium ring, or R3 and R4 together with the nitrogen atom to which they are attached, form a 5-or 6- membered ring containing one to three hetero atoms (in addition to N, one or two further N, O or S), which heterocyclic ring is unsubstituted or substituted by one or two C1-4alkyl groups, each Rs and R6 has independently one of significances of R3 and R4, except hydrogen, R7 is C1-4alkyl or benzyl with the exception that R7 is not benzyl when R5 and R6 have one of the cyclic significations of R3 and R4 or R5, R6 and R7 together with the nitrogen atom to which they are attached, form a pyridinium ring which is unsubstituted or substituted by one or two methyl groups, Q, is C2-8alkylene ; branched C28alkylene ; C2-6alkylene substituted by one or two hydroxy groups; C1 6alkylene-1, 3-phenylene ; or C, 6alkylene-1, 4-phenylene, Q2 is C2-8alkylene ; branched C28alkylene ; C3-6alkylene substituted by one or two hydroxy groups; C1-4alkylene-1,3-phenylene ; C1-6alkylene-1,4-phenylene ; 1,3- phenylene or 1,4-phenylene, Q3 is C2-8alkylene,

R8 is H; unsubstituted C, 6alkyl or C1-6alkyl monosubstituted by hydroxy, cyano, chlorine or phenyl, Rg is unsubstituted C1-6alkyl or C1-6alkyl monosubstituted by hydroxy, cyano or chlorine, and Ane is a non-chromophoric anion, E is NH or a direct bond, m is 0 or 1, and if m is 1 the phenyl group is substituded meta or para, n is 1 or 2 with the provisos that (i) when n is 1 then DK is a radical of formula (a) wherein Rio is S02-Y or-O-Y, where Y is a C2 4-alkenyl group or a C2-4alkyl group which is optionally substituted by -CN, -OH, -OSO3H, halogen or -NR11R12, wherein R"and R12 are independently from one another H, Cl. 4alkyl or substituted C1-4alkyl, or Ril and R12 together with the nitrogen atom to which they are attached, form a 5-or 6-membered ring containing one to three hetero atoms (in addition to N, one or two further N, O or S), which heterocyclic ring is unsubstituted or substituted by one or two C1-4alkyl groups preferably, R'ro and R"lo are independently from one another H; C1-2alkyl ; OC, 2alkyl ;-S03H ;-OH or-CN; or DK is a radical of formula (b)

wherein R13 is H; C1-4alkyl ; substituted C1-4alkyl ; O-C1-4alkyl ; substituted O-C1 4alkyl ;-SO3H ;-OH;-CN ; -COOR11 ; -NR11R12 or halogen, wherein Rf, and Rt2 have the same meanings as defined above, R, 4 and R, 5have the same definition as R, 3 with exception of hydrogen, wherein at least one of the Ris, Ri4 or Rr5 is-SO3H ; or DK can be a bicyclic ringsystem wherein each ring is independently from each other a 5-or 6-membered ring and the bicyclic ringsystem is not substituted by further azo groups and (ii) when n is 2 then DK is a divalent radical B, as well as their salts and/or mixtures thereof.

The compounds can be in internal or external salt form.

Any alkyl or alkylen present is linear or branched unless indicated to the contrary. In any hydroxy-or alkoxy-substituted alkyl or alkylen group, which is linked to a nitrogen atom, the hydroxy or alkoxy group is bound to a carbon atom other than to the

C,-atom. In any alkylen group substituted by two hydroxy groups, the hydroxy groups are bound to different carbon atoms.

It is preferred that the substituted triazinyl radical is attached to the naphthol radical at the 6 or 7 position.

If m is 1 the preferred substitution of the phenylen group of the [-N (R,)-C (O)-E-phenylene-]-group is meta.

It is also preferred that the sulphonic acid group is attached at the 3-position of the naphthol radical.

When DK is a bicyclic ringsystem then each ring can comprise one or more heteroatom, preferably N, O and/or S. Each ring can be aromatic or aliphatic. Each ring can be substituted.

Any alkyl as R, preferably contains 1 or 2 carbon atoms, and is more preferably methyl.

Any alkyl monosubstituted by hydroxy is preferably linear or branched C, 3alkyl.

R1 is preferably Ria, where each Ria is independently hydrogen; methyl ; ethyl or 2-hydroxy-ethyl.

Where X, or X2 is an aliphatic amino group, such group is preferably a mono (C1 4alkyl)- or di (C1 4alkyl)-amino group in which each alkyl group is independently unsubstituted or monosubstituted by halogen (particularly chlorine or bromine), C1 4alkoxy, phenyl or hydroxy, of which substituents hydroxy is most preferred. Any cycloaliphatic amino group as X, or X2 is preferably a C56cycloalkyl-amino group in which the cycloalkyl group is unsubstituted or substituted by one or two C1 2alkyl groups.

Where X, or X2 is an aromatic amino group, such group is preferably a phenylamino group in which the phenyl ring is unsubstituted or substituted by one or two groups selected from halogen (more preferably chlorine), C1 4alkyl, C1 4alkoxy, hydroxy and phenoxy.

Where X, or X2 is a heterocyclic amino group, it is preferably a saturated 5-or 6- membered ring containing one or two hetero atoms (that is in addition to N, O or S),

which heterocyclic ring is unsubstituted or substituted by one or two C, 4alkyl groups.

More preferably it is a piperidino-or morpholino-group.

Any unsubstituted C1 6alkyl group as R3 or R4 is preferably methyl or ethyl. Any substituted C2-6alkyl group as R3 or R4 is preferably ethyl or propyl monosubstituted by cyano or hydroxy with the substituent in the 2-or 3-position.

Any phenyl as R3 or R4 is preferably unsubstituted. Any phenylalkyl group is preferably benzyl, the phenyl ring of which is preferably unsubstituted. Any cycloalkyl as R3 or R4 is preferably cyclohexyl ; any alkylsubstituted cycloalkyl is preferably cyclohexyl substituted by one to three methyl groups.

R3 or R4 are preferably R3a or R4a, where each R3a or R4a is independently hydrogen ;. unsubstituted C, 4alkyl ; linear hydroxy-C2 3alkyl ; phenyl ; benzyl or a pyridinium ring.

More preferably, R3 or R4 are R3b or R4b, where each R3b or R4b is independently hydrogen; unsubstituted C, 4alkyl ; 2-hydroxethyl or a pyridinium ring.

Most preferably, R3 and R4 are R3c and R4c respectively, where each R3C and R4c is independently hydrogen; methyl or ethyl.

It is particularly preferred that R3 and R4 having a non-cyclic significance are identical groups.

Rs and R6 are preferably R5a and R6a respectively, where each R5a and R6a is independently unsubstituted Colza 4alkyl ; linear hydroxy-C23alkyl or benzoyl, or R5a and R6a together with the nitrogen to which they are attached form a piperidine-, morpholine-, piperazine-or N-methyl-piperazine-ring.

More preferably, Rs and R6 are R5b and R6b respectively where each R5b and Reb is independently unsubstituted C, 4alkyl or 2-hydroxy-ethyl.

Any alkyl as Ry is preferabfy methyi or ethyl, especially methyl.

In a preferred embodiment of the invention, Z above has the meaning Za, wherein each Za is independently a group selected from

in which p' is 0 or 1, R2b is H; methyl or 2-hydroxyethyl, Q1b is unsubstituted C2-6alkylene ; monohydroxy-substituted C3-4alkylene ; -(CH2)1-4-1,3- phenylene; -(CH2)1-4-1,4-phenylene ; 1,3-phenylene or 1,4-phenylene, each Q2b and Q3b is a linear C2-6alkylene group,

each R3b and R4b is independently H; unsubstituted C, 4alkyl or 2-hydroxy-ethyl, or a pyridinium ring, each R5b and R6b is independently unsubstituted C, 4alkyl or 2-hydroxy-ethyl, R7b is C1 4alkyl or benzyl or R5b,R6b and R7b together with the nitrogen to which they are attached form a pyridinium ring which is unsubstituted or substituted by one or two methyl groups, Ri3b is H; methyl ; ethyl or 2-hydroxyethyl, Rgb is methyl ; ethyl or 2-hydroxyethyl, Rio is in position 4, and An'is a non-chromophoric anion.

In preferred compounds of the invention Rio is a-SO2-Y or-O-Y radical, wherein Y is a C2. 4-alkyl group which is monosubstituted by-Cl,-OH or-OS03H.

In preferred compounds of the invention Rio is in position 4.

In further preferred compounds of the invention Rio is a -SO2-Y or-O-Y radical, wherein Y is a C2-4-alkyl group which is monosubstituted by -NR11R12, wherein R"and R,2 together with the nitrogen atom to which they are attached, form a 5-or 6-membered ring containing one to three hetero atoms (in addition to N, one or two further N or 0), which heterocyclic ring is unsubstituted.

In further preferred compounds of the invention R, 3 is H ;-CH3 or-OCH3.

In further preferred compounds of the invention R14 and R, 5 are independently from one another-CH3 ;-CH2CH3 ;-OCH3 ;-OCH2CH3 or-SO3H.

Preferred bicyclic ringsystems have the following formulae (c)- (i)

wherein R16, R, 7 and Ris are independently from each other H ; -SO3H ;-OH ; -NR11R12, wherein R11 and R12 have the same meanings as defined above; wherein Rig and R2o are independently from each other H;-OH; halogen ; Ci. 2alkyl or O-C, 2alkyl ; wherein R21 and R22are independently of one another are H; C, 4-alkyl ; phenyl or a substituted phenyl group having 1 to 5 substituents selected from the group consisting of C, 4-alkyl, C, 4-alkoxy, halogen, nitro, cyano, hydroxyl, CF3, CONH2, CONH(C5-6-cycloalkyl), CON (C, 4-alkyl) 2, CONH (C1-4)-alkyl, COO (C1-4)-alkyl, COO (C5 6-cycloalkyl) and CONH (phenyl), R23 is H; a trifluoromethyl group; a halogen atom; C1-4-alkyl; C1-4-alkoxy ; a nitro or a cyano group Rig is as defined above;

wherein R24 is H; methyl ; methoxy; ethoxy; chloro or bromo;

wherein R25 and R26 are independently from each other H; C, 4alkyl or substituted C, 4alkyl, Rig is as defined above;

wherein A is S or O and Rig is as defined above;

wherein A is S or O and Rig is as defined above. as well as their salts and mixtures thereof.

Preferably the-N=N-group is in formula (h) and (i) in the para-position.

In further preferred compounds of the present invention, when n is 2 and B is one of the following divalent radicals

wherein each T is independently from one another a direct bond; a C1 4alkylene group; a substituted C-14alklylene group; a C2-4alkenylene group or a substituted C2-4alkenylene group, V is one of the following radicals

each R, and each Rig and each T has the meanings as defined above.

Especially preferred compounds according to the present invention have the following formula wherein DK is one of the radicals (a) to (i) as defined above wherein Rio is SO2Y or-O-Y wherein Y is a O2-4 alkyl group which is substituted by -OH or Y is a C2-4-alkyl group which is monosubstituted by-NRllRl2, wherein Ri, and R12 together with the nitrogen atom to which they are attached, form a 5-or 6-membered ring containing one or two hetero atoms (in addition to N, one further N or 0), which heterocyclic ring is unsubstituted.

R'10 and R"io are independently from one another H; C1-2alkyl or OC, 2alkyl, R11 and R12 independently from each other are H ;-CH3 or-CH2CH3, R, 3 is H ;-CH3 or OCH3, R14 and R15 are independently from each other are-CH3 ;-CH2CH3 ;-OCH3 ; -OCH2CH3 or-SO3H, R16, R17 and Ris are independently from each other H ;-NH2 ;-OH or-SO3H, Rig and R20 are independently from each other H ;-CH3 or-OCH3, R2, and R22 are independently from each other H ;-CH3 or-CH2CH3, R23 is H ;-CH3 or-CH2CH3, R24 is H ;-CH3 or-OCH3, R25 and R26 are independently from each other H ;-CH3 or-CH2CH3, X, and X2 are independently from each other a group Za as defined above. Further especially preferred compounds according to the present invention have the following formula

wherein DK is a divalent radical B which can be chosen from the group consisting of

where V is one of the following radicals

each R1 and each Rig has the meanings as defined above and wherein each T is independently from one another a direct bond; a C1-4alkylene group; a substituted C1-4alkylene group; a C24alkenylene group or a substituted C24alkenylene group, as defined above, and X, and X2 are independently from each other a group Za as defined above.

The present invention further provides a process for the preparation of compounds of formula ()) comprising reacting the diazonium salt of an amine of formula (II), DK-NH2 (II) in which DK is as above defined and preferably being so positioned as above defined, so as to give a preferred compound of formula (I) as above disclosed, with a compound of formula (III), in which Ri, Xi, and X2 are as above defined.

When DK is B, the mole concentration of compound (III) has to be at least twice the mole concentration of compound (II).

Diazotisation and coupling may be effected in accordance with conventional methods.

The coupling reaction advantageously is carried out in an aqueous reaction medium in a temperature range of from 0-60°C, preferably at 20-50°C, and in a pH range of from 3 to 9, preferably at pH 4 to 6. All temperatures are given in degrees Celsius.

The reaction mixtures comprising compounds of formula (I) thus obtained may be converted into stable liquid formulations with improved long term stability by desalting by ultra filtration.

The compounds of formula (I) thus obtained may be isolated in accordance with known methods.

The compounds of formula (I) containing free basic groups may be converted wholly or in part into water-soluble salts by reacting with any inorganic or organic acids for example with lactic acid, or acetic acid, or formic acid, or with hydrochloric acid, or with sulfuric acid.

The starting compounds, the amines of formula (II), are either known or may be prepared in accordance with known methods from available starting materials. The compounds of formula (III) may be prepared by step-wise replacement of the chlorine atoms of cyanuric chloride whereby in a first and second step, cyanuric chloride is reacted with a diamine of formulae (IV) and (V) (as hereinafter defined), respectively, in which R2b is as above defined and Q and X have the following meanings: Q may have any of the meanings of Ql, Q2 or Q3 above; and X has the meaning of X,.

In the case where identical diamino groups have to be introduced, this first and second step may be combined into one step. Suitably, the single step is carried out at temperatures of from 0-30°C and preferably at pH 4-6.

Where different diamino groups have to be introduced, suitably, the diamine showing the higher selectivity with respect to the condensation reaction is introduced in the first step at a temperature of preferably 0-20°C more preferably 0-5°C. Both condensation steps may be carried out using the conventional reaction medium where the upper limit of pH is 7. The second step is preferably carried out at 10-40°C, more preferably 12-30°C.

The final third step, the condensation with the aminonaphthol component, is carried out at elevated temperatures in the range of 60-100°C and at pH 2-3.

The starting compounds of formulae (IV) and (V) are either known or may be prepared in accordance with known methods from available starting materials.

The compounds according to the invention, in acid addition salt form or quaternary ammonium salt form, may be used for dyeing cationic dyeable materials such as: homo-or mixed-polymers of acrylonitrile, acid modified polyester or polyamide ; wool ; leather including low affinity vegetable-tanned leather ; cotton; bast fibers such as hemp, flax, sisal, jute, coir and straw; regenerated cellulose fibers, glass or glass products comprising glass fibers; and substrates comprising cellulose for example paper and cotton. They may also be used for printing fibers, filaments and textiles comprising any of the above mentioned materials in accordance with known methods.

Printing may be effected by impregnation of the material to be printed with a suitable printing paste comprising one or more compounds of the present invention. The type of printing paste employed, may vary depending on the material to be printed. Choice of a suitable commercially available printing paste or production of a suitable paste, is routine for one skilled in the art. Alternatively the compounds of the present invention may be used in the preparation of inks suitable for example for jet printing, in accordance with conventional methods.

Most preferably, the dyestuffs are used for dyeing or printing of paper e. g., sized or unsized, wood-free or wood-containing paper or paper-based products such as cardboard. They may be used in continuous dyeing in the stock, dyeing in the size press, in a conventional dipping or surface coloring process. The dyeing and printing of paper is effected by known methods.

The dyeings and prints and particularly those obtained on paper, show good fastness properties.

The compounds of formula (I) may be converted into dyeing preparations. Processing into stable liquid, preferably aqueous, or solid (granulated or powder form) dyeing preparations may take place in a generally known manner. Advantageously suitable liquid dyeing preparations may be made by dissolving the dyestuff in suitable solvents such as mineral acids or organic acids, e. g., hydrochloric acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, lactic acid, glycolic acid, citric acid and methanesulphonic acid. Furthermore formamide, dimethylformamide, urea, glycols and ethers thereof, dextrin or addition products of boric acid with sorbit may be used together with water, optionally adding an assistant, e. g. a stabilizer. Such preparations may be obtained, for example, as described in French patent specification No.

1,572,030.

The compounds of formula (I) (in the corresponding salt form) have good solubility especially in cold water. Owing to their high substantivity the compounds of the present invention exhaust practically quantitatively and show a good build-up power. They can be added to the stock directly, i. e. without previously dissolving, as either a dry powder or granulate, without reducing the brilliance or the yield of color. They can also be used in soft water without loss of yield. They do not mottle when applied on paper, are not inclined to give two-sided dyeing on paper and are practically insensitive to filler or pH variations. They operate over a broad pH range, in the range of from pH 3 to 10. When producing sized or unsized paper, the wastewater is essentially colorless. This feature, which is extremely important from an environmental viewpoint, when compared with similar known dyes, shows a marked improvement. A sized paper dyeing when compared with the corresponding unsized paper dyeing does not show any decrease in strength.

The paper dyeings or printings made with the compounds according to the invention are clear and brilliant and have good light fastness. On exposure to light for a long time, the shade of the dyeing fades tone in tone. They show very good wet fastness properties; being fast to water, milk, fruit juice, sweetened mineral water, tonic water, soap and sodium chloride solution, urine etc. Furthermore, they have good alcohol fastness properties. The wet fastness properties are improved compared to known

dyes showing otherwise similar properties. They do not exhibit a tendency towards two- sidedness.

Paper dyed or printed with the compounds of the present invention can be bleached either oxidatively or reductively, a feature, which is important for the recycling of waste paper and old paper products.

The compounds of the present invention may also be used to dye paper containing wood-pulp where even dyeings, having good fastness properties are obtained.

Furthermore, they may be used for the production of coated paper in accordance with known methods. Preferably when coating, a suitable filler, for example kaolin, is employed in order to give a one-side coated paper.

The compounds of the present invention are also suitable for dyeing in combination with other dyes for example other cationic or anionic dyes. The compatibility of the compounds of the present invention when used as a dye in mixtures with other commercially available dyes, may be determined according to conventional methods.

The thus obtained dyeings have good fastness properties.

The invention yet further provides use of a compound of the present invention for dyeing or printing any of the abovementioned substrates.

The invention further provides a substrate, which has been dyed or printed with a compound of the present invention. The substrate may be selected from any of the above mentioned substrates. A preferred substrate is a substrate comprising cellulose such as cotton or paper or paper based product.

The following examples further serve to illustrate the invention. In the Examples all parts and all percentages are by weight or volume, and the temperatures given are in degrees Celsius, unless indicated to the contrary.

EXAMPLE 1 168.5 parts 4- (2-hydroxyethoxy)-aniline are mixed with 1760 parts of water and 293 parts of a 30% solution of hydrochloric acid and are diazotized at 0-5°C during 1 hour with 286.2 parts of a 4 n solution of sodium nitrite. During 1 hour the reaction mixture is then pumped to 4803 parts of an aqueous solution containing 534.2 parts of a coupling component of the following formula : During the coupling reaction a pH of 4.5-5 is kept by the addition of a 30% solution of sodium hydroxide. The reaction mixture is stirred at room temperature and pH 4.5-5 for additional 10-14 hours. After rising the pH value to 8.2, the precipitated dyestuff is filtered off and washed with 2000 parts of a 5% solution of sodium bicarbonate, 1000 parts of a 2% solution of sodium bicarbonate and 2000 parts of a 1% solution of sodium bicarbonate. 2043.1 parts dyestuff presscake of the following formula are obtained (titer ca. 31,4%): Xmax = 512 nm in 1% acetic acid)

EXAMPLE 1a 33.5 parts of the dyestuff presscake from example 1 are dried at 80°C in vacuum over night and are milled to obtain 11.5 parts of a dyestuff powder. It dyes sized and unsized paper in scarlet shades. The obtained fastnesses are excellent.

EXAMPLE 1 b 300 parts of the dyestuff presscake from example 1 are added at 60-65°C to a mixture of 100 parts of formic acid and 600 parts of water and are stirred for additional 30 min.

16 parts of Hyflo-Supercel (filtration auxiliary) are added at 60-65°C and after 10 min stirring the mixture is filtered. 1000 parts of a long term stable liquid dyestuff formulation are obtained. It dyes sized or unsized paper in scarlet shades. The obtained fastnesses are excellent.

TABLE 1 (Examples 2-108) In an analogous manner as described in Examples 1,1 a and 1 b using the appropriate starting material, further compounds of formula (I) are produced. The compounds have the formula in which the symbols have the meaning given in the following table. No. DK Shade 2 0 NH2 orange H chus s 3 NH 2 scarlet H CH 3 HO 3s H03S 4 N NH scarlet 5 H CHs 0 5 aN NH 2 scarlet Cl H c S H 3 H. CS' 6 H NrCHS scarlet H I \- c H I U- 8 nu 2 red I 0 0 9 O -NNHs red H ! kA 10 HO S-O ^/NH2 scar (et CL 3 11 HO S-O Hs scarlet H 12 so3 H scarlet H I H3C0 \ 13 OCH3 ^/NH2 scarlet H03S H CH3 Hic 14 OCH3 scarlet H03S H Hic H3c 15 HO,, o C2H4-OH scarlet ^-N C2H4 OH 16 HO S-O_ ^//NH4 oH scarlet CH4 oh C-OH 17 \/\o C2H3 scarlet \ /\ n 2''S c HO S-O-HNiHs scarlet 3 19 so3 H N-*C2N scarlet H c C2F 20 T, , NH2 scarlet po H 3 21 scarlet // - N H 22 H3S- scarlet o \/ '--'--N H 23 S03H r scarlet Nl. H3C0 \/-N fui 24 scarlet o \/ - N H H 25 Hp3S-O o scarlet - nez H H 26 S03H o scarlet H3CO N H H 27 =<SO3H () H scarlet H I H3CO < C2H4-OH 28 scarlet holz O -H N 29 H3S- scarlet -H 30 S03H scarlet .-non H3C0 \ 31 H scarlet 0 nua y H 32 H violet z -N H 33 H 3c red N ZON NUA 34 HsC-N/Nzf"s red N NEZ NID 35 N I -H/ i zHs red N : 0= JJ i H 35C,. ''ed 0=< N H H 3 6 H C tC H 3 gH r e d o H H 37 H ci red o H 38 N I OH-H/ i zHs violet O H H n -39 H<oOMe N/NI violet o H 40 H NH2 scarlet HN H CHg 0 0 41 H N H violet r, H CH3 H zona 42 Hic NH red N H nez N H H 43 H3Cm N/>/red Nid N H 93\ H CH3 H H 44 N ^/NH2 red N H CHs H 45 N red O I \ N - N ZON 46 N red o I O N % \ H-nez H 47 H red \-N N O II l H I N ,-OH H 4$ O N O-CH/\ violet 3 H H 0 H-N H O NH AH4-OH GzHa OH Na H 50 H 50 o N scarlet han N HN I/N J .. _-N O H 51 N H4- scarlet 0 y Na H HN C, OH 0 52 H MH red H H CH3 . H CHg H 53 o H C2H red zon H H H 54 IH 0 scarlet --N N --l NHZ 55 scarlet --OH OH 56 H red o- -CONH N, 2 H ou zon H 58 H violet H --nu2 0 N) H o N o-CH violet OXN O-CH3 0 nua H 60 H scartet - N N 0 N) a HAN 61 H scarlet 0y Na OU 0 62 H red 0 zona O N H H 63 H red NUN /oh H H 64 O-CH 3 NH2 orange - nez HOS \/H CH3 ici d- 65 O-CH 3 orange 0. -N N HID H 0 66 O-CH3 NH2 orange O HO S 0-0-3 Hic 67-CH3 orange 0. -N N O Hic H3c 68 scarlet OH H CH 3 OH 69 C2F scarlet 3 H I Oh 70 CH 3 NH 2 scarlet I 70CH''''NH'scartet H H CH 3 71 CH3 ^/NH2 scarlet - N up. N H C 3 72 NH 2 scarlet N H CH 3 N O 73 H C\ ^ . NH2 scarlet s fV ! O-, CH3 H CH3 74 o) * HNzNn CH3 scarlet CH3 75 * HNNCH3 scarlet zon * CH3 78 CH3 scarlet *HN NH2 NHZ 7$ CH3 scarlet L1 ;"3 nu2 79HNNCH3 scariet * i CH3 80 HO J\3 red , N,, , I N Nz Ho-' 82 0 CH 3 scarlet H, 04 * CH3 82 o CH3 scarlet *HN NHZ 3 cH3 orange H3 HaCs * *HN., J\ 3 84 o CH3 scarlet N) L'-' *HN"'NH2 cl HIC 85 o CH3 scarlet t)/\ t 2 c3 CH, 86 o = CH3 scarlet * *HNNHZ 87 0-cH3 scarlet 88 o = CH3 scarlet 1 UN3 88 0 CH3 scarlet H3c *HNI-NH2 CHEZ 89 o CH3 scarlet N-v * *HNNH HNJ 89 o =. CH, scar) et HNJ 90 o CH3 scarlet r N \ NH, H3C NJ HC 91 o CH3 scarlet N°'\J* 'N 0 °9 92 JX * HN/\NtCH scarlet \ CH3 /* 93 ° * HNNcH scarlet 3 hic °-* HNN^CH3 scarlet CH3 CH3 CH, 95 0 * HNN^CH3 scarlet H2* CH3 96 0 * HNNcH scariet 3 3 CH3 CH3 97 O HNN^CN3 scariet H3C N JC < CH3 Hic ° *N1VN^CN3 scarlet r'N) CH3 HNJ - * HNNCH3 scarlet r'N) CH3 . J HgC 100 0 * HNN^GH3 scarlet n/\ * -\CHg . O 101 * NNcN scarlet 01 N * CH3 H C 3 102 CH3 scarlet * *HN v _NH hic H, C 104 CH3 scarlet 3 S CHg 104/\ 3 scartet 104/=\ CH3 scarlet * *N v _NH < CH, 105 * NrwcH scarlet 3 N * CH3 NI H13c, N 106 CH3 scarlet 'N * *HNNH H3c, NJ H * HNN^CH SCat'I2t w rN-- CH3 HNJ HNJ 108 CH3 scarlet fsN~ < *HN\ßNH2 z NJ

EXAMPLE 109 61.3 parts 4- (2-hydroxyethoxy)-aniline are mixed with 640 parts of water and 106.5 parts of a 30% solution of hydrochloric acid and diazotized at 0-5°C during 1 hour with 102.4 parts of a 4 n solution of sodium nitrite. During 1 hour the reaction mixture is pumped to 1560 parts of an aqueous solution containing 228.4 parts of a coupling component of the following formula:

During the coupling reaction a pH of 4.5-5 is kept by the addition of a 15 % solution of sodium carbonate. The reaction mixture is stirred at room temperature and at pH 4.5- 5 for additional 10-14 hours. After adjusting the pH value to 4.0, ca. 800 parts of sodium chloride are added in portions. The precipitated dyestuff is filtered off to a yield of 692.5 parts dyestuff presscake. After drying for 12 hours at 80°C 429 parts of a dyestuff of the following formula are obtained (may = 513 nm in 1% acetic acid):

It dyes sized or unsized paper in scarlet shades. The obtained fastnesses are excellent.

TABLE 2 (Examples 110-160) In an analogous manner as described in Example 109 using the appropriate starting material, further compounds of formula (I) are produced. The compounds have the formula in which the symbols have the meaning given in the following table. No. DK X1 Xz Shade 110 H NH red Cl 3 N H CH3 H H 111 N CH3 NH2-NN red Cl H H CH3 112 H cl NH red i H H H H 113 H OH NH violet \- H CH, c N N' 3 H CH3 114 N pMe NH2-NNz violet cl H N H 115 o N NH2-N//NzHs scarlet y-NZ---H I HN 0 116 H NH red 3 H O N H 117 H NH violet 3 NZ^ " 3 O N H 118 0 H3 orange o)- H CH, c, HIC HIC 119 CH3 NH scarlet H3c o \/H ICH H Hs H CH3 120 HN'N"'CH CH3 scarlet *HN * C s NHZ * HNNCH3 cH3 scarlet I *HN L ; N3 NH2 122'*NHsCH, scariet *HN nu 123 0 HN-CH3 CH3 scarlet *HN \/* NH 124 0 *HN^CH H3 scarlet *HN NH2 125 0 *HN CH3 scarlet ! * HN *HN 1 * NHZ 1 26 o) N*~OH CH3 scariet OH _3 NH2 127 SN N'CH3 scarlet O N *HN Cl3 2 128 0 OH CH scarlet '*HN * * HN'v OH 129 oa t CH3 scarlet 0 CH3 NH2 N \/p * CH3 NHZ 130 0. cH3 scarlet N'N-- * HN 131 0 --1 cH3 scarlet NN *HN * OH NHZ 132 0 H3 CH3 cH3 scarlet *HN HN* NH NH2 H CH3 133 H, c cH CH, scartet I * HN'NH C s H, C CH, 134 CH3 * NN-CN3 cH3 scarlet i 1 3 3 H, C CH, 135 CH3 CH3 scarlet 3 H3c 0-0 *HN I'NH 2 \CH3 HgC 0- * 'NH 'S'P'. HN-NCH, scar) et 136 NH2 *HN CH3 scarlet * * HN NHz 137 *HN-CH 3 CH scarlet *HN NH2 138 _ * HNPN CH3 CH3 scarlet *HN CH3 NH2 139 *HN CH3 *HN CH3 scarlet 1-NH 2 NHZ Q-tJ- 39 * HN/OH CH3 scarlet Nu2 G N"Z NON c3 scarlet \. LOH NHZ 141'/-\ OH cH, scariet *HN-, NH 2 CH3 NHZ 142 OH CH scarlet OH *HN * HN NN2 '3 cITV'NPscahet 144/\/-\ CHg scartet *HN-, CHU NHZ 144 _ scarlet No * * NH2 NH2 G 145 n/\ CH3 scarlet \-OH NH2 -OH NNZ HN* NH CH3 \ HN* NH HgCCH3 147 H 3C CH3 *HN CH 3 scarlet HN* NH-, NH 2 HN"NN NHZ H3CCH3 * HNN^CH CHa scarlet O 3 *HN'\ I \ CH3 NHZ 149 * HNN^CH CHa scarlet CNJC icHN v _NHZ H3C 150 * HNN^CH CH3 scariet NO * 3 * HN \ < 2 * H CH, 151 0 * HNN^CH CH3 scar (et H2NJX X CH3 * HNJ 152 0 * HNN) CH3 CH3 scarlet CH CH3 * HNJ\NH2 CL, 3 CH3 153 * HNZN) CH3 CH3 scarlet H3C^N-v H3 *HN v'NHz H3c) 154 0 * HNN^CH CHa scarlet CNJX X CH3 * HNJ\NH2 HUI 155 old * HN N CH3 CH 3 scarlet r 0 \CH3 *HN"-NH 2 nu 2 H3C 9 156 0 CH scarlet * HN'N'CH 3 z 01-) 157 o/= * HNVNN CH3 CH3 scarlet *HN 0 . N' CH3 NHz H3C 158 * HNN^CH3 CH3 scarlet CH CH3 *HNNH cl 3 CH, 159 * HNN) CH3 CH3 scarlet 3 r X CH3 *HNXJ\NH2 H3C 9 3 160 * HNZ NN CH3 CH3 scarlet CN~ < CH3 *HNSJ\NH2 HNJ

EXAMPLE 161 12.2 parts 1,2 bis (4-aminophenoxy) ethane are mixed with 250 parts of water and 40 parts of a 30% solution of hydrochloric acid and are diazotized at 0-5°C during 1 hour with 25.7 parts of a 4 n solution of sodium nitrite. During 1 hour, the reaction mixture is pumped to 405 parts of an aqueous solution containing 50.9 parts of a coupling component of the following formula :

During the coupling reaction a pH of 4.5-5 is kept by the addition of a 15% solution of sodium carbonate. The reaction mixture is stirred at room temperature and pH 4.5-5 for additional 10-14 hours. The precipitated dyestuff is filtered off to yield 241.7 parts dyestuff presscake. After drying for 12 h at 80°C 83.3 parts of a dyestuff of the following formula are obtained (may = 556 nm in 1% acetic acid):

It dyes sized and unsized paper in red shades. The obtained fastness properties are excellent.

TABLE 3 (Examples 162-180) In an analogous manner as described in Example 161 using the appropriate starting material, further compounds of formula (I) are produced. The compounds have the formula No. DK'X Shade 162/NzHs red H O 0 163/=\ ,, red HN H I oi-6 O 164 H red N z N H-0- 165 0 red N -H-- N 166 0 red WN v N H-0- 0 SrH-- 0 167 orange --N 0 po O O 168 orange --N 0 po O O 169 0 0 orange o \/H I o L /=\- 0', 0 0 0 o'c 170 o/=\-.. orange 0 1 H po \/ , 0 o o 171 * HNN--^ cH3 scarlet 113C * J2 CHs 172 CH3 scarlet H3C N+----0-0*12 *HN 1- N H2 173 CH3 H3C CH3 scarlet *HN O-NH I I */\ S HH lOSI Cl3 hic CH3 H3C 174 OCH3 HaC, *HN'N^CH3 scarlet 0 0 CH 3 11 11 -S-N N-S *$ S HH ISOI 00 0-0- CH, H, C 175 H3 H3, cH3 scarlet * 0 *HN loollH H 11 S-NN-S /* O O CH3 H3C 176 CH H3C * HN/\NN CH3 scariet ÇIL 0 ci3 H H 11 S-N N-S -* Ouzo CH3 H3C 177 llX) scariet *HN 0 <-- "NH, .. Hic Hic H 3c HC 178H3C * HNNACH scariet 0 0 CH 3 * i H 3c N N S-0 11 12 0 H3C 179 H3C CH3 scarlet *HN p N HZ Hj-fyi N 11 o H, C * HNN CH3 scarlet 0 razz H3CN. N N S H3c, N-S Hic

Example 181 11.7 parts 1-Dimethylamino-2- (4-aminophenoxy)-ethane are mixed with 150 parts of water and 27 parts of a 30% solution of hydrochloric acid and diazotized at 0-5 °C during 1 hour with 15. 8 parts of a 4 n solution of sodium nitrite. Afterwards 46.5 parts of a coupling component of the following formula was added:

During the coupling reaction at room temperature first a pH of 4.0-4.5 is kept for 2 hours and then for 12 hours at 5.5-6.0 by the addition of 100 parts of a 15% solution of sodium carbonate. The precipitated dyestuff is filtered off to yield 138. 6 parts dyestuff presscake. After drying for 12 hours at 60°C 60.9 parts o a dystuff of the following formula are obtained (amas= 511 nm in 1% acetic acid):

TABLE 4 (Examples 182-202) In an analogous manner as described in Example 181 using the appropriate starting material, further compounds of formula (I) are produced. The compounds have the formula No. DK X Shade red 3 182 N * HNN CH3 H3C O / CH red 183 *HN CH3 183 G' *HN red red HN"N"CH3 u /"\ CH, red 185 N * HN NH red 186 N'/\ * * HNN-^- CH3 186 \CH3 cl3 rend O l CN3 187 NO * *HNNH rend 188 CN o. red CH red c3 red 189 HO *HNI-"NH2 HO red 190 HO HN Nn 3 red CH3 HO-' H red 191 oy *HN H/* NHZ red ou H rend H N CH 3 H O-CH, redish 193 n-* HN /-'S * NHZ HO p o-CH3 redish 193 HO<Ot 9\3 orange 11 HO-l p o-CHg red 194 CH 3 195 HO/--S * * HN NU her o-cH red 0 HN""-' 196 s hic O rend 0 red 197 *HNNH /=\ CH3 orange 198 H3C, *HN 3 2 c3 red 199 HO o * * HN\JsNH red NHZ red \/CHg He. HO o * * HN/\Nn CH3 red red CH 201 C, CH 3 red 201 *HN red 202 H3CNO<E 7 3 red I uti3

TABLE 5 (Examples 203-212) In an analogous manner as described in Example 181 using the appropriate starting material, further compounds of formula (I) are produced. The compounds have the formula No. DK X, X2 Shade Rend CH3 ^ C,'H3 * HNN- CH3 * HN 203 H3c CH3 *HN NH2 red 204 GN~OE * HN n 3 l red CH3 NH2 cl3 rend 205 GN~OX3 * HN n 3 \< NH red CH3 NH2 rend O 1 ^ CH3 208 HN'-N CH CH * CH3 NHZ CH, NH2 H C * HNN^CH 207 3 \N * CH33 *HNNHZ CH3 CH3 red /;- CH 6d 208 HO HN" N CH3 *HN CH3 red CH3 * HN NHZ Ho bluish 209 0= HN' 3 *HN /* CH3 NH2 H Q-CH, scar ! et CH3 210 11 * HN"NfCH3 *HN -S \/* CH3 NHZ Ho-/0 o,-CH3 red 0 CH XHNN-- CH3 HN 211 H-o * cH3 * hic HsC 212 Ho o ç * 7 3 XJ\3 (X CH3 *CHNNH z

APPLICATION EXAMPLE A 70 parts chemically bleached sulphite cellulose obtained from pinewood and 30 parts chemically bleached cellulose obtained from birchwood are beaten in 2000 parts water in a Hollande. 0.2 parts of the dyestuff of Example 1 a are sprinkled into this pulp. After mixing for 10 min, paper is produced from this pulp. The absorbent paper obtained in this way is dyed a brilliant scarlet red. The wastewater is colorless.

APPLICATION EXAMPLE B 0.2 parts of the dyestuff powder according to Example 1a, were dissolved in 100 parts hot water and cooled to room temperature. The solution is added to 100 parts chemically bleached sulphite cellulose which have been ground with 2000 parts water in a Hollande. After 15 minutes thorough mixing resin size and aluminium sulphate are added thereto. Paper produced in this way has a brilliant scarlet red nuance and exhibits perfect light and wet fastness.

APPLICATION EXAMPLE C An absorbent length of unsized paper is drawn at 40-50°C through a dyestuff solution having the following composition: 0.3 parts of the dyestuff according to Example 1 a 0.5 parts of starch and 99.0 parts of water.

The excess dyestuff solution is squeezed out through two rollers. The dried length of paper is dyed a brilliant scarlet red shade.

The dyestuffs of Examples 2 to 212 as well as mixtures of Examples 1 a-212 may also be used for dyeing by a method analogous to that of Application Examples A to C. The paper dyeings obtained show good fastness properties.

APPLICATION EXAMPLE D 0.2 Parts of the dyestuff of Example 1 a in acid addition salt form are dissolved in 4000 part of demineralised water at 40°C. 100 Parts of a pre-wetted cotton textile substrate are added, and the bath is raised to the boiling point over 30 minutes and held at the boil for one hour. Any water, which evaporates during dyeing, is replaced continuously. The dyed substrate is removed form the bath, and after rinsing and drying, a brilliant scarlet red dyeing is obtained having good light-and wet-fastness properties. The dyestuff exhausts practically totally onto the fiber, and the wastewater is almost colorless.

In a similar manner as described in Application Example D the dyestuffs according to Examples 2-212 as well as mixtures of Examples 1a-212 may be used for dyeing cotton.

APPLICATION EXAMPLE E 100 parts freshly tanned and neutralized chrome leather are agitated for 30 minutes in a vessel with a liquor consisting of 250 parts of water at 55°C and 0.5 parts of the dyestuff of Example 1 a in acid addition salt form, and then treated in the same bath for 30 minutes with 2 parts of an anionic fatty liquor based on sulphonated train oil. The leather is then dried and prepared in the normal way, giving a leather evenly dyed in a brilliant scarlet red shade.

By a method analogous to that described in Application Example E the dyestuffs according to Examples 2-212 may be used for dyeing leather.

Further vegetable-tanned leathers of low affinity may be dyed using the dyestuffs as described herein in accordance with known methods.

APPLICATION EXAMPLE F Water is added to a dry pulp in Hollander consisting of 60% (by weight) of mechanical wood pulp and 40% (by weight) of unbleached sulphite cellulose, and the slurry is beaten in order to obtain a dry content slightly exceeding 2.5% and having a beating degree of 40° SR (degrees Schopper-Riegler). The slurry is then exactly adjusted to a high density dry content of 2.5% by adding water. 5 Parts of a 2.5% aqueous solution of the dyestuff according to Example 1a are added to 200 parts of the above resulting slurry. The mixture is stirred for about 5 minutes and, after the addition of 2% (by weight) resin size and then 4% (by weight) alum (based on the dry weight) is further stirred for a few minutes until homogeneous.

The resulting pulp is diluted with about 500 parts water to a volume of 700 parts and then used for the production of paper sheets by suction on a sheet former. The resulting paper sheets are dyed a brilliant scarlet red.

By a method analogous to that described in Application Example F any one of the dyestuffs of Examples 2-212 as well as mixtures of Examples 1a-212 may be used instead of that of Example 1a. In all cases, the waste paper exhibits a substantially low residual dye concentration.

APPLICATION EXAMPLE G Water is added to a dry pulp in a Hollander consisting of 50% (by weight) of chemically bleached sulphite cellulose obtained from pinewood and 50% (by weight) of chemically bleached sulphite cellulose obtained from birchwood, and the slurry is ground until a degree of grinding of 35° SR is reached. The slurry is then adjusted to a high density dry content of 2.5% by adding water, and the pH of this suspension is adjusted to 7.10 Parts of a 0.5% aqueous solution of the dyestuff according to Example 1 a are added to 200 parts of the above resulting slurry, and the mixture is stirred for 5 minutes. The resulting pulp is diluted with 500 parts water and then used for the production of sheets by suction on a sheet former. The paper sheets thus obtained have a brilliant scarlet red.

By a method analogous to that described in Application Example G further dye mixtures may be used consisting of any one of the dyestuffs of Examples 2-212. In all cases, paper sheets are formed having a brilliant scarlet red shade.

APPLICATION EXAMPLE H 12.6 parts dyestuff of Example 1 are added dropwise at room temperature to a stirred mixture of 20.0 parts diethyleneglycole and 67.4 parts of demineralized water. The resulting ink exhibits good light-and waterfastness properties. In a similar manner as described in Application Example H all the Examples of Table 1 and Table 2 and Table 3 and Table 4 and Table 5 may be used.