DE4139319A1 - New vinyl-sulphonyl-alkyl aniline cpds. - Google Patents

Abstract

New reactive dyestuffs (I) contain vinylsulphonyl(alkyl)anilino-s-triazinylamino gp(s). or precursors. New N-ethyl-, N-propyl- and N-beta-hydroxyethyl-vinyl-, beta-chloroethyl-, beta-hydroxyethyl- and beta-sulphatoethyl-sulphonyl-(m)ethyl-, -prop-2-yl or -propyl-aniline cpds. (II) are of formulae (I), (II) (where D = the radical of an organic dyestuff; B = a direct bond or a bridging gp. to a ring C atom of an aromatic carbocyclic or a ring C or N atoms of an aromatic heterocyclic ring in D; Ra and Rb independently = H or an 1-4C alkyl gp., opt. substd. by OH, CN, CO2H, OSO3H or SO3H; U = Cl, F or a pyridinium gp., opt. substd. by CO2H, CO2NH2, SO3H or 1-4C alkyl; W = linear or branched 1-6C alkylene; Y = CH=CH2 or CH2-CH2-X; X = a gp. eliminated by alkali; V = H, halogen, 1-4C alkoxy, 1-3C alkyl, CN, COOH, SO3H or CONH2; D = the radical of formazan, phthalocyanine, anthraquinone or triphenodioxazine dyestuff if (a) W = -CH2-; or (b) U = Cl and W = 2C alkylene; M = Et, Pr or C2H5OH; V1 = H, Cl, SO3H, Me, CO2H or OMe; L = Ch=CH2 or CH2-CH2-Q; Q = Cl, OH or -OSO3H; W1 = CH2, C2H4, -CH2-CHMe- or -(CH2)3).

Description

The present invention relates to novel water-soluble reactive dyes, processes for their preparation and their use for dyeing.

The practice of dyeing with reactive dyes has been increasing in recent years Requirements for quality and cost-effectiveness of dyeing processes. As a result, there remains a need for new reactive dyes that have improved properties in terms of fastness and processability. From EP-A 3 07 817 and JP-A 72 23 708 are already reactive dyes Basis of azo dyes known which have two reactive groups.

The present invention relates to novel reactive dyes of the formula

wherein
D = residual organic dye,
B = direct bond or bridge member to a ring C atom of an aromatic carbocyclic or to a ring C atom or N atom of an aromatic heterocyclic ring in D,
R _a , R _b = identical or different, H, C₁-C₄-alkyl or with OH, CN, CO₂H, OSO₃H or SO₃H substituted C₁-C₄-alkyl,
U = Cl, F or an optionally substituted by CO₂H, CONH₂, SO₃H or C₁-C₄-alkyl pyridinium,
W = straight-chain or branched C₁-C₆-alkylene,
Y = CH = CH₂ or CH₂-CH₂-X, wherein
X = alkaline eliminable radical,
V = H, halogen, C₁-C₄-alkoxy, C₁-C₃-alkyl, CN, COOH, CONH₂
or
with the proviso that

• a) D = the radical of a dye of the formazan, phthalocyanine, anthraquinone and triphendioxazine series when W = -CH₂-, and
• b) D = the radical of a dye of the formazan, phthalocanine, anthraquinone and triphendioxazine series or
  U = F or an optionally substituted by CO₂H, CONH₂, SO₃H or C₁-C₄-alkyl pyridinium,

when the radical W is C₂-alkylene.

D is preferably the radical of an organic dye of mono- or polyazo, Metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, Dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, Nitroaryl, naphthoquinone, pyrenchinone or perylenetetracarbimide series.

X is preferably OSO₃H, SSO₃H, OCOCH₃, OPO₃H₂, OSO₂CH₃, SCN, NHSO₂CH₃, Cl, F, Br, OCOC₆H₅, OSO₂-C₆H₄CH₃N⊕ (CH₃) ₃; if W = -CH₂-, X is in particular OSO₃H, Cl, Br, F.

Suitable bridge members B, which may be the same or different, are for example:

the star marks the point of attachment with D,
R has a meaning mentioned under R _a ,
Alk optionally by heteroatoms, such as O, S,

interrupted, straight-chain or branched C₁-C₆-alkylene,
Ar optionally substituted phenylene or naphthylene and
Alk or Ar may contain further substituents, for example F, Cl, Br, C₁-C₄-alkyl, C₁-C₄-alkoxy, carboxy or sulfo.

The radical D in formula (1) can be substituted in the usual way his. As examples of other substituents may be mentioned at the radical D: alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl or Butyl, alkoxy groups having 1 to 4 carbon atoms such as Methoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups with 1 to 8 carbon atoms, such as acetylamino, Propionylamino or benzoylamino, amino, alkylamino with 1 to 4 carbon atoms, such as methylamino, Ethylamino, propylamino, isopropylamino or butylamino, Phenylamino, N, N-di-β-hydroxyethylamino, N, N-di-β-  sulfato-ethylamino, sulfobenzylamino, N, N-disulfobenzylamino, Alkoxycarbonyl having 1 to 4 carbon atoms in the Alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl, Alkylsulfonyl having 1 to 4 carbon atoms such as methylsulfonyl or ethylsulfonyl, trifluoromethyl, nitro, Cyano, halogen, such as fluorine, chlorine or bromine, carbamoyl, N-alkylcarbamoyl having 1 to 4 carbon atoms in the Alkyl radical such as N-methylcarbamoyl or N-ethylcarbamoyl, Sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms such as N-methylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, N- (4-hydroxyethyl) - sulfamoyl, N, N-di (β-hydroxyethyl) sulfamoyl, N- Phenylsulfamoyl, ureido, hydroxy, carboxy, sulfomethyl or sulfo. Preferably, the radical D contains one or several sulfonic acid groups. Reactive dyes of the formula (1) wherein D is the residue of an azo dye as substituents especially methyl, ethyl, methoxy, Ethoxy, acetylamino, benzoylamino, amino, chloro, bromo, Ureido, hydroxy, carboxy, sulfomethyl or sulfo.

The radical R _a and R _b in formula (1) is, if it is an alkyl radical, straight-chain or branched; he may be further substituted, for. By halogen, hydroxy, cyano, C _1-4 alkoxy, carboxy or sulfo. Examples of R are the following radicals: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, carboxymethyl, β-carboxyethyl, β-carboxypropyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, β-methoxyethyl, β-ethoxyethyl, β-methoxypropyl, β-chloroethyl, γ-bromopropyl, β-hydroxyethyl, β-hydroxybutyl, β-cyanoethyl, sulfomethyl, β-sulfoethyl, aminosulfonylmethyl and β-sulfatoethyl.

Suitable bridge members W are, for example

Preferred dyes are those of the formula

wherein
B, D = have the abovementioned meaning,
R _a = identical or different, H or C₁-C₂-alkyl,
R _{b is} H, C₁-C₃-alkyl, β-hydroxyethyl, β-sulfatoethyl, β-carboxyethyl, β-cyanoethyl or carboxymethyl,
U = Cl, F or an optionally substituted by CO₂H, CONH₂, SO₃H or C₁-C₄-alkyl pyridinium,

Y = CH = CH₂ or CH₂-CH₂-X, with
X = Cl or OSO₃H,
V = H, Cl, C₁-C₂-alkyl, C₁-C₂-alkoxy, COOH, SO₃H.

Preferred dyes are those of the formulas (4) to (8th)

wherein
R _{a is} H or C₁-C₂-alkyl,
Pc phthalocyanine core,
Me divalent metal ion, for example Fe, Cu, Zn, Co, Ni, preferably Cu, Ni,
n 0 or 1,
u + v + w = 3-4, with the proviso that
w = 0.8-2.0,
v = 0-1.0,
u = 1.0-3.0,
A₁ = aliphatic, araliphatic or aromatic bridge member,
G = oxygen or -N-R₁₁, wherein
R₁₁ = H, C₁-C₂-alkyl, wherein when A₁ = C₂-alkylene, R₁₁ and R _a may be closed to a ring,
T₁, T₂ = H, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy or acylamino,
R₁-R₆ = independently of one another H, C₁-C₄-alkyl, C₁-C₄alkoxy, hydroxy, halogen, carboxy, sulfonamido, alkyl- or arylcarbonylamino, or -sulfonylamino, β-sulfatoethylsulfonyl or SO₃H,
R₇-R₁₀ = H, C₁-C₂-alkyl, optionally substituted by hydroxy, carboxy or sulfonyl, wherein R₉ and R₁₀ may also be closed to form a ring, when A₁ = C₂-alkylene,
Z = a radical of the formula

wherein
U = Cl, F or an optionally substituted by CO₂H, CO₂NH₂, SO₃H or C₁-C₄-alkyl pyridinium,
A = a radical of the formula

wherein
R _b = H, C₂H₅, i-C₃H₇, n-C₃H₇, C₂H₄-OH, carboxy methyl, carboxyethyl or β-cyanoethyl

V is H, SO₃H, COOH, C₁-C₂-alkyl, C₁-C₂-alkoxy, Cl,
Y = CH = CH₂ or CH₂-CH₂-X
with X = Cl or OSO₃H.

Particularly suitable aliphatic radicals A₁ are C₂-C₈- Alkylene radicals represented by heteroatoms or Heteroatomgruppierungen interrupted or substituted can, for example

Particularly suitable araliphatic radicals A₁ are C₁-C₄- Alkylenphenylreste by heteroatoms or heteroatom groups can be interrupted, such as

Particularly suitable aromatic radicals A₁ are phenylene radicals, substituted by substituents, such as C₁-C₂-alkyl, SO₃H or COOH may be substituted, as for example

Particularly preferred are copper formazan dyes of Formulas (9) - (12)

in which
R _a = H, C₁-C₂-alkyl,
Z has the abovementioned meaning of the formula (2a) and the total number of sulfo groups in the dye is at least 2.

Very particular preference is given to copper formazan dyes the formula

in which mean
U = F, Cl or an optionally substituted by CO₂H, CO₂NH₂, SO₃H or C₁-C₄-alkyl pyridinium,

wherein V, W and R _{b have} the meaning given under formula (3a).

Further particularly preferred are phthalocyanine dyes of the formula (13)

in which
Z, Pc, u, v, w have the abovementioned meaning,
Me = Cu or Ni,
A₁ = C₂-C₄-alkylene, 1,3-phenylene, 1,3-sulfophenylene or 1,3-carboxyphenylene.

Further particularly preferred are triphendioxazine dyes of the formulas (14) and (15)

in which
Z = radical of the formula (2a)
R _a = H or C₁-C₂-alkyl
G = O, N-R₁₁ (with R₁₁ = H, C₁-C₂-alkyl, where, when A₁ = C₂H₄ R _a 'and R₁₁ can also be closed in a ring),
T₁, T₂ = Cl or Br mean.

Also particularly preferred are anthraquinone dyes of Formula (16)

wherein
R _a = H, C₁-C₂-alkyl,
Z = radical of the formula (2a),
R₁₂H, C₁-C₄alkyl, alkoxy, halogen, CO₂H or SO₃H,
R₁₃-R₁₅ independently H, C₁-C₄-alkyl or SO₃H.

Also preferred are dyes of the following formulas (17) - (28):
wherein
B has the meaning given above,
R _a = H, C₁-C₂-alkyl,
Z = remainder of the formula

wherein
U = F, pyridinium, which may be substituted by COOH, CONH₂, SO₃H or C₁-C₄-alkyl
and

wherein
R _b = H, CH₃, C₂H₅, i-C₃H₇, nC₃H₇, C₂H₄OH, carboxymethyl, carboxyethyl

V, Y have the meaning given under formula (3a).

R₁₆ alkyl, alkoxy, halogen,
R₁₇ H, alkyl, aryl, hetaryl, aralkyl,
R₁₈ COOH, CH₃

R₁₆ alkyl, alkoxy, halogen,
R₁₇ alkyl, aralkyl, aryl,
R₁₈ alkyl, aryl, aralkyl, hetaryl,

R₁₆ alkyl, alkoxy, halogen,
R₂₀H, alkyl, alkoxy, acylamino, amino,
o, p in o- or p-position to the azo group

R₁₆ alkyl, alkoxy, halogen,
R₂₀ alkyl, alkoxy, arylamino,
o ortho to the azo group,
R₂₁H, C₁-C₂-alkyl, acylamino, ureido,
R₂₂ R₈, NO₂,

R₁₆ alkyl, alkoxy, halogen,
K remainder of a coupling component, wherein, in particular, those of the pyridone, pyrazolone, acetoacetic arylidene and naphtholsulfonic acid series come into question as coupling components.

With
R₂₃ alkyl, halogen,
R₁₆ alkyl, alkoxy,
K remainder of a coupling component,

R₁₆ alkyl, alkoxy, arylamino,

R₁₆ alkyl, alkoxy,
R₂₄ H, NH₂, arylamino.

The present invention further relates to the preparation of the reactive dyes of the formula (1) according to known methods.

The following should be mentioned.

• 1. The preparation of the reactive dyes is carried out by condensation of a color base of the general formula DB-NR _a -H (29) in which D, B and R _{a have} the abovementioned meaning, with 2,4,6-trichloro- or 2,4, 6-trifluorotriazine.
  The intermediate is in a further reaction step with an aminosulfone of the formula in which R _b , V, Y, W have the abovementioned meaning,
  converted to the reactive dye.
• 2. The preparation of the dyes of the formula (1) can also be carried out by condensing a dye base of the general formula (29), in which D has the abovementioned meaning, with the fiber-reactive compound of the formula (31), W, U, _Rb , V, Y are as defined above.
• 3. Suitable dye precursors are with Trihalogentriazinen and the Components of the formula (30) or suitable precursors are used with the Condensed primary condensation products of formula (31) and then ßend converted into the dyes.
• 4. Optionally, in the synthesized Halogentriazinfarbstoff the Exchanged halogen atom with the rest of a pyridine, which is replaced by COOH, CONH₂, SO₃H, C₁-C₄-alkyl may be substituted.

The condensations of the starting components with the Trihalogentriazinen and the components of the formula (30) or with the reactive components of the formula (31) are carried out independently of the order in aqueous or organic aq gen media in the presence of acid-binding agents. Depending on the Nature of the starting components takes place in the first stage of condensation in pH ranges from 2 to 8, preferably 3 to 7, and at temperatures from 0 to 40 ° C, preferably 0 to 25 ° C. The replacement of the second halogen atom of the Triazine takes place in the pH range of 4 to 10, preferably 5 to 9, and in Temperature range from 0 to 60 ° C, preferably 0 to 30 ° C.

Acid-binding agents are, for example, carbonates, hydroxides or phosphates such as Sodium carbonate, sodium bicarbonate, dilute sodium hydroxide, di- or Trisodium phosphate or sodium fluoride.

Should the condensation or the dye synthesis directly to a dye solution or lead to a liquid dye preparation, the use of Lithium carbonates or lithium hydroxide may be advantageous, if appropriate together with solubilizers and / or stabilizing buffer systems. Other conversion reactions of the dyes or their precursors such Metallization reactions, sulfations or introduction of acylamino group in general, in any stage of the dye synthesis be made.  

Particularly valuable dyes of this series are water-soluble formazan, Anthraquinone, triphendioxazine and phthalocyanine as well as azo dyes, and in particular those which have sulfonic acid and / or carboxylic acid groups. The Dyes can be both metal-free and metal-containing, wherein among the Metal complexes, the copper, nickel, chromium and cobalt complexes preferred Own interest.

Suitable dye radicals D or the dyes of the formula (1) on which lying amino-containing color bases are in the literature in very large numbers described. By way of example may be mentioned here:

DE-A 25 57 141 Color bases of Formulas 9-11 DE-A 32 39 364 A1 Farrb bases of formula 12 DOS 1 64 463 Color bases of formula 13 US 40 07 164 @ DOS 25 03 011 Color bases of formulas 14-15 DOS 21 24 080 @ DOS 34 23 581 @ U. Venkataram Color bases of formula 16 "The Chemistry of Synthetic Dyes", @ Vol. III, Academic Press, New York, 1952

Further examples are given in the following literature:
EP-A 54 515, EP-A 69 703, EP-A 70 807, EP-A 73 267, DE-A 32 22 726, DE-A 25 57 141, DE-A 26 50 555, DE-A 30 23 855, DE-A 28 47 938, DE-A 28 17 780, GB-A 20 57 479, DE-A 29 16 715, DE-A 28 14 206, DE-A 30 19 936, EP-A 45 488 and Venkataraman: The Chemistry of Synthetic Dyes, BD. VI, Chapter II, pp. 211-325, New York, London; 1,972th

The invention also relates to the novel amines of the formula

wherein
M = C₂H₅, C₃H₇, C₂H₅OH,
V¹ = H, Cl, SO₃H, CH₃, CO₂H, OCH₃,
L = CH = CH₂, CH₂-CH₂-Q,
Q = Cl, OH, -OSO₃H,

The preparation of the new amines of formula (32) is carried out according to known methods:
Nitro or acylamino compounds of the formula (33)

wherein
V¹, W¹ = have the abovementioned meaning,
E = NO₂ or acylamino,

be in a conventional manner with 2-mercaptoethanol to sulfides of the formula

wherein
E, V¹ and W¹ have the abovementioned meaning,
reacted and these in a known manner, for example with H₂O₂ or chlorine, to give sulfones of the formula (35)

wherein
V¹, W¹ have the abovementioned meaning,
Q¹ is HO or Cl,
oxidized and then reduced the nitro group E or saponified the acylamino E. The resulting known amino compounds of the formula (36)

wherein
V¹, W¹ have the abovementioned meaning,
are N-alkylated in a known manner (eg by reductive alkylation). Optionally, then, the OH group is converted into Q¹ in a -OSO₃H group (in a known manner with concentrated sulfuric acid or oleum). By the action of oleum, in addition to the sulfato groups, additional sulfo groups (V 1 = SO 3 H) can be introduced into the phenylene radical. The amines thus obtained can be converted by treatment with alkaline agents, such as alkali metal hydroxide or alkali carbonate, into compounds of the formula (32) in which the grouping L is the grouping -CH = CH₂.

The construction of compounds of formula (35) with E = NO₂ can also starting of compounds of the formula

wherein
W¹, Y¹ have the abovementioned meaning, and
V² = H, C₁-C₂-alkyl,
by reaction with 2-mercaptoethanol and subsequent oxidation to compounds of the formula

wherein
V², W¹, Q¹ have the abovementioned meaning
and subsequent nitration of the compounds (38) to give compounds of formula (35) with E = NO₂. For example, OH groups Q¹ esterified during the nitration can be converted back to OH groups by saponification. When introducing the nitro group via the compounds of formula (38) arise in general with respect to the position of the nitro group to the side chain W¹-SO₂-CH₂-CH₂-Q¹ isomer mixtures.

An important and special variant for the preparation of compounds of the formula (38) or (35) consists of the radical-catalyzed addition of 2-mercapto ethanol to styrenes or allyl benzenes of the formula

wherein
E¹ = H, NO₂,
R _c , R _d = H, C₁-C₂-alkyl, and
V² has the meaning given above,
the subsequent oxidation of the resulting sulfides of the formula

with the meanings given for E¹, V², R _c , R _d to give sulfones of the formula

wherein
E¹, V², R _c , R _{d have} the abovementioned meaning, and
Q¹ = OH, Cl
and optionally subsequent nitration, that is, with the conversion of E¹ = H to E¹ = NO₂ the conversion to compounds of formula (35).

In a further preferred embodiment, the invention relates to a method for the preparation of amines according to claim 11 (with W = C₂H₄), characterized characterized in that one reacts with ethenylaromatics of the formula (33a)

wherein
E¹ = H, NO₂ or acylamino, and
Y¹ has the meaning given under formula (33), 2-mercaptoethanol to sulfides of the formula (34a)

radically catalysed added,
these to sulfones of the formula (35a)

wherein
Q¹ has the meaning given in claim 10, oxidized and then, when E¹ = H nitrated to E¹ = NO₂, the nitro group E¹ reduced or the acylamino E¹ saponified, optionally the resulting amino compounds N-alkylated and / or the OH group Q¹ in converts an OSO₃H group and optionally in the phenyl nucleus in place of V¹ = H introduces a SO₃H group.

Particularly suitable amines of the formula (30) for the reaction with 2,4,6-trichloro- or 2,4,6-trifluorotriazine or with a precondensation product of the color bases of the formula (29) with the above-mentioned triazine are, for example wise:

The dyes according to the invention are outstandingly suitable for dyeing and Printing of natural and synthetic hydroxyl or amide group-containing Materials, in particular those of cellulose and polyamides. dye mixtures Dyes of formula (1) have improved solubility properties.

Both the dyes and the dye mixtures are particularly suitable for Dyeing of cellulosic materials in exhaust, pad, cold and continuous procedure, as well as in print.

The dyes of the invention, in particular the general formula (1) are suitable excellent in blends with other dyes, especially for Trichromien.

The reactive dyes of the formula (1) are characterized by high reactivity and excellent fixability. Due to their bifunctionality they result also from long fleet high Fixierausbeuten. They are characterized by relative Independence of fertility from the dyeing temperature and therefore can after the exhaust process used at low to medium dyeing temperatures become. In the pad-steaming process, they only require short steaming times. you give colorings of high color strength with good light and wet fastness properties.

The stated dye formulas are those of the free acids. In the preparation of In general, the salts are obtained, in particular the alkali metal salts such as Sodium, potassium or lithium salts. The dyes can also be considered concentrated Solutions are used.

Example 1

65 g of the sodium salt of the compound of the formula

are dissolved in 200 ml of water at pH 7.5. One cools to 0 ° C and leaves in 20 minutes 9 g trifluorotriazine drip while keeping the pH level by adding Sodal solution at 6-7. After completion of the implementation is a neutralized solution of 17.5 g of 4-aminobenzyl-β- Sulfatoethylsulfon added dropwise in 100 ml of water and the pH was kept at 7 with soda solution. After finished Condensation, the dye is either by a steaming or spray drying or by salting out isolated. The dye of the formula thus obtained  

λ _max = 611 nm
dyes cotton in real blue tones.

example 2

Another valuable dye is obtained when you instead of the color base used in Example 1, the Na triumsalz of the compound of the formula

used and otherwise discolored analogously. That's how it is tene dye of the formula  

λ _max = 589 nm
dyes cotton in real blue tones.

Example 3

Working analogously to Example 1 and substitutes of 4-aminobenzyl- (β-sulfatoethyl) -sulfone the 4- [N- ethyl] aminobenzyl- (β-sulfatoethyl) sulfone one the dye of the formula

λ _max = 612 nm
the cotton according to the usual reactive dye application methods in blue shades.

example 4

Working analogously to Example 3 and substitutes of 2,4,6-trifluorotriazine, 2,4,6-trichlorotriazine, to obtain a dye of the formula

λ _max = 613 nm
the cotton in accordance with the dyeing methods customary for reactive dyes in blue shades.

Examples 5 to 36

Further valuable dyes according to the invention are obtained according to the information of Example 1 by implementing the in Table 1 specified components.

The resulting dyes have very good fiber break tive dye properties and deliver after the üb intensive dyeing and printing processes Dyeings and prints with those in the respective tables example given color on cotton.  

Table 1

Examples 42 to 50

Further dyes according to the invention of the general formula

can be analogous to the embodiment by order tion of the components indicated in Table 2 produce.

The resulting dyes have very good fiber break tive dye properties and deliver after the üb intensive dyeing and printing processes Dyeings and prints with in the respective tables example given color on cotton.  

example 51

32.9 g of copper phthalocyanine compound of the formula

prepared by condensation of copper phthalocyanine tetrasulfochloride sulfonic acid with 3-aminoacetanilide and Ammonia and subsequent saponification of the acetylamino group in dilute sodium hydroxide solution at 75 ° C 420 ml of water at pH 7 dissolved. The solution is dripped in 30 minutes to a suspension, which is made from a solution of 5.9 g of cyanuric chloride in 50 ml of acetone and 50 g of ice has produced, and keeps in the reaction mixture, the temperature to 0 to 3 ° C, the pH by dosing 2n soda solution at 4.0 to 4.5. After 30 minutes since the end the addition of the resulting solution is clarified and with 10.7 g of 4-aminobenzyl-β-sulfatoethylsulfone added. By adding further soda, the condensation at pH 6.0 to 6.5 and performed at 15 to 23 ° C. The obtained Dye is either by evaporation or Spray drying or by salting out with 70 g of sodium chloride and filtration isolated from the solution. He corresponds to the formula  

λ _max , = 668 nm, 629 nm in H₂O
and dyes cotton from long liquor or after the well-known block process in turquoise blue tones.

A similar dye is obtained when replacing the color base used at the outset 33.9 g of copper phthalocyanine compound the formula

used and otherwise proceeds analogously. The dye thus obtained shows an absorption of λ _max = 668 nm, 629 nm in H₂O.

example 52

28.3 g of copper phthalocyanine compound of the formula

prepared by condensation of copper phthalocyanine tetrasulfochloride sulfonic acid with monoacetylethylenediamine and subsequent hydrolytic cleavage of the Acetylrestes with dilute sodium hydroxide solution at 75 ° C, be dissolved in 380 ml of water at pH 8.5. The solution will be in Dripped for 30 minutes to a suspension by pouring a solution of 7.2 g of cyanuric chloride in 45 ml Acetone is obtained on 45 g of ice. One stops in the reaction mixture the pH by adding 2N sodium hydroxide solution to 7.0 to 7.5 and the temperature to 0 to 5 ° C. To After stirring for 1 hour, the solution is clarified and the Filtrate in portions with 11.5 g of 4-aminobenzyl-β-sulfatoethylsulfon added. During the littering and Thereafter, the pH is maintained in the reaction mixture 6.0 to 6.5, initially raising the temperature to 20 to 25 ° C and after 2 hours to 30 ° C.

After completion of the condensation of the dye from the Salted solution with sodium chloride, filtered with suction and at Dried at 50 ° C in a vacuum. It corresponds to the formula

λ _max = 668 nm, 629 nm in H₂₀
and gives on cotton turquoise dyeings and prints.

Similar dyes are obtained when replacing above copper phthalocyanine compound 28.4 g of copper phthalocyanine compound the formula

or
33.7 g of copper phthalocyanine compound of the formula

starts.  

example 53

10.9 g of 4-aminobenzyl-β-sulfatoethylsulfon be in Dissolved 150 ml of water at pH 5.5. It is 0.3 g Sodium fluoride to the solution and cooled to 0-3 ° C from. With good stirring, 6.1 g of cyanuric fluoride are now run in and maintains the pH with dilute soda solution on 4,5. After a short stirring, the condensation is completed.

32 g of copper phthalocyanine component of the formula

prepared according to the specifications of the European patent specification 00 73 267, in 300 ml of water at pH = 7.0 -7.5 solved. Now let the solution of the above Condensation product to the dye component at 0-5 ° and keeps the pH in the reaction mixture to 7.0 to 7.5. After 3 hours you leave the Temperature gradually rises to 20 ° C and continues to hold the pH constant. After completion of the implementation the product obtained is salted out of solution, aspirated, buffered with a little phosphate solution at pH 6.0 and dried in vacuo at 45 ° C. The dye corresponds the formula  

and dyes cotton from long liquor and after the well-known Continuous process in turquoise tones.

Further phthalocyanine reactive dyes are obtained by condensing the metal phthalocyanine components and reactive components mentioned in Table 3 in an analogous manner.

example 61

40 g of 1-amino-4- (2'-aminomethyl-4'-methyl-6'-sulfophenylamino) - anthraquinone-2-sulfonic acid are dissolved in 800 ml Water and 100 ml of acetone by neutralization with approx. 54 ml of 2N sodium hydroxide solution dissolved at pH 7. It is cooled to 10 ° C and drops a solution of 17.5 g of cyanuric chloride in 100 ml of acetone in 15 to 20 minutes. During the dripping keeping the pH in the reaction mixture 2N soda solution at 6.0 to 7.0. If the soda consumption about 1 hour after the cyanuric chloride addition to a standstill has come, one leaves a neutralized solution of 26.6 g of 4-aminobenzyl-β-sulfatoethylsulfone in 270 ml Water at 20 ° C, keeps the pH with soda solution to 6.5 and raises the temperature to 25-30 ° C. After condensation, the dye is through Salted out, isolated and at 50 ° C in a vacuum dried. It corresponds to the formula

λ _max = 626 nm, 588 in H₂O
and gives brilliant reddish blue dyeings and prints on cellulosic fibers according to the known padding and printing processes.

example 62

53.1 g of 1-amino-4- (3'-amino-5'-sulfo-2 ', 4', 6'-trimethyl-phenylamino) - Anthraquinone-2-sulfonic acid will be available in 530 Dissolve water at pH 6. 19.4 g of cyanuric chloride are dissolved in 100 ml of methyl ethyl ketone and the solution discharged on 100 g of ice. Now let the dye solution to the cyanuric chloride suspension at 0-10 ° C is added dropwise and keeps in the reaction mixture with 10% sodium carbonate solution the pH to 4.5. After completion of the implementation A neutralized solution of 31.0 g of 4-aminobenzyl β-sulfatoethylsulfone in 310 ml of water dosed and at a temperature of 20-25 ° C, the pH with dilute sodium carbonate solution to 5.8 to 6.0, until the Condensation is finished. The resulting dye of formula

is isolated by salting out and filtration and at Dried at 50 ° C in a vacuum.

He gives brilliant reddish blue on cotton Dyeings and prints.  

A similar dye is obtained when replacing of 4-aminobenzyl-β-sulfatoethylsulfone the same Amount of 3-aminobenzyl-β-sulfatoethylsulfon used.

example 63

14.7 g of 1-amino-4- (3'-amino-phenylamino) -anthraquinone 2,4'-disulfonic acid in 250 ml of water at pH 5 and 0-5 ° C solved. 2.8 ml of cyanuric fluoride are allowed inside from 5 to 10 minutes to the solution of the color component drops and keeps the pH at 4.2 with 2N soda solution to 4.7. After a short stirring, the condensation is Difluorotriazinyl dye terminated.

9.8 g of 4-aminobenzyl-β-sulfatoethylsulfon become the Solution of the reactive dye component added slowly while maintaining the pH at 5.0 to 5.6. Thereafter, the pH is maintained at 6.0 to 6.5 and allowed in the course from 15 hours the temperature gradually to 20 ° C rise, after which the condensation is completed. The Dye is now in the course of 2 hours with 8% Salted out potassium chloride. Man sucks the precipitated Dye of the formula

λ _max = 602 nm in H₂O
Wash with 10% potassium chloride solution until light. After drying in vacuo at 45 ° C to obtain a product with the cellulose tissue can be dyed and printed in blue shades.

example 64

13.2 g of 4-aminobenzyl-β-sulfatoethylsulfon be in 250 ml of water dissolved. After cooling the solution up 0-5 ° C, a pH of 4.5 is set. you Leaves 4.2 ml of cyanuric fluoride within 15 minutes to the Drop solution and keeps with 2N soda solution the pH to 4.0 to 4.5. To the suspension of the obtained Reactive component will become one within 30 minutes neutralized solution of 19.0 g of 1-amino-4- (3'-amino-2'- methylphenylamino) anthraquinone-2,5'-disulfonic acid in 350 ml of water added dropwise. One keeps in the reaction solution the temperature continues to 0 to 5 ° C and the pH with soda solution to 6.0 to 6.5. After 2 hours The temperature is gradually lowered within 15 hours rise to 10 ° C. After completion of the condensation becomes the dye of the formula

salted out of the solution with 10% sodium chloride, filtered off, washed with 10% sodium chloride solution and dried at 45 ° C in a vacuum.

With the dye can be cellulose fibers in clear dye and print blue tones.

example 65

Substituting in Example 64 instead of the specified there Anthrachinonkomponente a neutralized solution of 20.4 g of 1-amino-4- (4'-methyl-aminomethyl-phenylamino) - anthraquinone-2,2'-disulfonic acid with the condensation product of 13.6 g of 4-aminophenyl-β-sulfatoethylsulfone and 4.4 ml of cyanuric fluoride at 0 to 5 ° C and pH 6.5 to 7.0 microns and works as described there, so receives a dye of the formula

λ _max = 597 nm, about 625 nm in H₂O
which also gives clear blue dyeings and prints on cotton according to the usual techniques.

example 66

9.6 g of cyanuric chloride are dissolved in 50 ml of acetone. The Solution is added to 50 g of ice and then allowed to neutralize Solution of 14.8 g of 4-aminobenzyl-β-sulfatoethylsulfone in 200 ml of water. One leads the Condensation by dropwise addition of 10% soda solution at pH 4.5 to 4.7, while keeping the temperature 0-5 ° C, after condensation to 15-20 ° C.

17.6 g Triphendioxazinverbindung the formula

in 600 ml of water by adjusting a pH of 9 dissolved with 2N sodium hydroxide solution. You give to the solution now in portions the above reactive component and holds in the reaction mixture, the pH with 2N sodium hydroxide solution 8.5 to 8.7, the temperature at 15 to 20 ° C. After completion the reaction becomes the dye of the formula

salted out, filtered off and dried in vacuo at 50 ° C. He gives on cotton according to the known dyeing techniques strong blue dyeings.

Further triphendioxin reactive dyes are obtained by reacting the following components:

example 69

27.3 g of 3,9-diamino-6,13-dichloro-triphendioxazine-4,11- disulfonic acid in 900 ml of water by neutralization dissolved with 10% lithium hydroxide solution. To Cool the solution to 0-5 ° C is added dropwise 10.8 g Cyanuric fluoride and holds with 10% lithium hydroxide Solution the pH to 5.5 to 6.0. Is the implementation 23.6 g of 4-aminobenzyl-β are added in portions. Sulfatoethylsulfon in the solution and keeps the pH Value continues at 6.0 to 6.5. After 5 hours you leave the Temperature with further pH control overnight Rise to 20-25 ° C. The solution is added with the addition of 1 g diatomaceous earth clarified, the dye from the filtrate salted out by addition of 15% sodium chloride and after filtration with suction and washing with 15% sodium chloride Solution dried at 50 ° C in a vacuum.

The dye of the formula

dyes cotton in strong reddish blue tones.  

example 70

Analogously to Example 69, the following are obtained Triphendioxazine dye:

It dyes cotton in strong reddish blue tones.  

example 70a

To a dye solution synthesized according to Example 1 was 3.0 g of pyridine-3-carboxylic acid. The solution is warmed to 75-80 ° and brings the pH with 2N soda solution to 7.0, until the exchange of the fluorine atom finished against the nicotinic acid residue. After cooling the dye can be salted out or the solution after desalting and concentrating as a liquid dye be used.

The dye corresponds to the formula

and colors similarly to the dye of Example 1 Cotton from a long fleet.

Similarly, the others in the previous ones Examples described fluoro- or chlorotriazine dyes into the 3-carboxypyridiniumtriazine Dyes are converted.  

example 71

10 g of 4-aminobenzyl (β-hydroxyethyl) sulfone (prepared according to GB 8 77 250 [C.A. 56; 11 758i]) are in autoclave in 100 ml of methanol after addition of 3.5 g of acetaldehyde and 4 g of Raney nickel under a hydrogen pressure of 60 to 80 bar set. The autoclave is heated to 40 ° C and maintains the hydrogen pressure until the Reaction is completed. The autoclave content is with 100 ml of methanol and the suspension boiling hot cleared of nickel. Crystallized from the filtrate at Concentrate the amine of the formula

which is filtered off with suction from the cooled mixture and can be washed with a little cold methanol.
1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.17 (t, 3H), 3.03 (m, 4H), 3.79 (q, 2H), 4.21 (s, 2H), 5.16 (t, NH), 5.61 (t, OH), 6.57 (d, 2H), 7.09 (d, 2H) ppm.

example 72

The procedure is as in Example 71 and substitutes for 4-aminobenzyl- (β-hydroxyethyl) -sulfone 5-amino-2- chlorobenzyl (β-hydroxyethyl) sulfone (manufactured EP 3 07 817 A1), the amine of the formula

1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.18 (t, 3H), 3.01 (q, 2H), 3.24 (t, 2H), 3.83 (t, 2H), 4.56 (s, 2H), 6.59 (dd, 1H), 6.77 (d, 1H), 7.19 (d, 1H) ppm.

Example 73

Instead of the 4-aminobenzyl (β-hydroxyethyl) sulfone can also be the same Process of 3-aminobenzyl (β-hydroxyethyl) sulfone in the amine of the formula

convict.
1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.18 (t, 3H), 3.05 (m, 2H), 3.14 (t, 2H), 3.81 (t, 2H), 4.31 (s, 2H), 5.22 (br, NH), 5.62 (t, OH), 6.55 (m, 3H) 7.08 (t, 1H) ppm.

In an analogous manner, the following compounds receive:

1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.13 (t, 3H), 2.95 (q, 2H), 3.11 (t, 2H),
3.65 (s, 3H), 3.75 (q, 2H), 4.26 (s, 2H),
5.00 (t, OH), 5.15 (br, NH), 6.46 (dd, 1H),
6.51 (d, 1H), 6.76 (d, 1H) ppm.

1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.18 (t, 3H), 2.20 (s, 3H), 3.00 (m, 2H),
3.26 (t, 2H), 3.84 (q, 2H), 4.40 (s, 2H),
5.20 (t, NH), 5.40 (t, OH), 6.46 (dd, 1H),
6.54 (d, 1H), 6.92 (d, 1H) ppm.

example 74

Instead of the acetaldehyde used in Example 72 the alkylation can also be carried out with n-propylaldehyde. An amine of the formula is then obtained

1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 0.95 (t, 3H), 1.55 (q, 2H), 2.92 (q, 2H), 3.24 (t, 2H), 3.81 (q, 2H), 4.50 (s, 2H), 5.19 (t, NH), 5.87 (t, OH), 6.58 (dd, 1H), 6.71 (d, 1H), 7.14 (d, 1H) ppm.

In an analogous manner, the following compounds are obtained:

Example 75

30 g of 4- [N-ethyl] aminobenzyl (β-hydroxyethyl) sulfone of Example 71 is in 90 ml of 100% sulfuric acid at 0 to 10 ° C registered. Stir for 2 hours and carry the resulting solution in 350 g of ice. The crystalline Precipitation is filtered off with 25% sodium chloride solution washed until free of sulphate and at 50 ° C in Vacuum dried. The product obtained corresponds to the formula

1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.22 (t, 3H), 3.35 (m, 4H), 4.18 (t, 2H), 4.56 (s, 2H), 7.58 (m, 4H), 9.48 (br, NH) ppm.

In an analogous manner, the following amines are obtained:

1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.20 (t, 3H), 3.27 (q, 2H), 3.58 (t, 2H), 4.19 (t, 2H), 4.68 (s, 2H), 7.32 (dd, 1H), 7.46 (d, 1H), 7.60 (d, 1H), 9.10 (br, NH) ppm.

1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.13 (t, 3H), 2.97 (m, 2H), 3.30 (t, 2H), 4.09 (t, 2H), 4.27 (s, 2H), 6.08 (m, 1H), 6.45 (m, 2H), 6.98 (m, 1H) ppm.

1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.20 (t, 3H), 2.41 (s, 3H), 3.38 (m, 2H), 3.58 (t, 2H), 4.20 (t, 2H), 4.65 (s, 2H), 7.40 (m, 3H) ppm.

1 H-NMR in D₆-DMSO (TMS as internal standard):
δ = 1.21 (t, 3H), 3.35 (q, 2H), 3.45 (t, 2H), 3.89 (s, 3H), 4.15 (t, 3H), 4.56 (s, 3H), 7.23 (d, 1H), 7.52 (m, 2H) ppm.

Example 76

78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (as monosodium salt) are dissolved in 800 ml of water at pH 6.5. After cooling to 0 ° C is allowed rapidly add 21.5 ml of cyanuric fluoride and keeps the pH at 20% Sodalösung to 4.0 to 4.5, the temperature further to 0 ° C.

72 g component of the formula

in 500 ml of water by adding 55 ml of 10% lithium hydroxide solution dissolved at 0 to 3 ° C to the pH of 6.9. You give both solutions together and keeps the pH in the reaction mixture at 5.0 to 5.2 with 2N sodium carbonate solution.

51.3 g of 2-aminonaphthalene-1-sulfonic acid are dissolved in 575 ml of water by neutralization dissolved with sodium hydroxide solution at pH 6.5 and 0 ° C. You give 57.5 ml concentrated Hydrochloric acid in a cast and then diazotized with 57.5 ml of 4 N sodium nitrite solution. After one hour of stirring, if necessary, excess Nitrite destroyed with amidosulfonic acid solution.

The resulting diazo suspension is now in the solution prepared above at 0 to 5 ° C while the pH in the mixture with 2 N sodium carbonate solution to 7.0 held. After 3 hours, the temperature is allowed to rise to 20 ° C and stirred until to end the clutch after. The resulting dye of the formula

is salted out with sodium chloride, isolated and after addition of something Phosphate buffer dried at 50 ° C in a vacuum.

It dyes from long liquor with an optimal dyeing temperature of 50 ° C in bluish red shades with high fixation yields.
λ _max = 546 nm in the water.

Example 77

78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are prepared as in Example 76 reacted with 21.5 ml of cyanuric fluoride. Then one is neutralized to pH 6, cooled to 0 to 3 ° C solution of 89.5 g of the component of the formula

obtained according to the example of 80, within a few minutes to and keeps the pH at 5.2 with 2N sodium carbonate solution.

When the condensation is complete, add a diazo suspension which is added prepared according to Example 76 from 51.3 g of 2-aminonaphthalene-1-sulfonic acid. Holds in the coupling mixture, the pH with sodium carbonate solution to 7.0 to 7.5. One lets gradually increase the temperature to 10 ° C in 2.5 hours and then to 20 ° C overnight increase, keeping the pH further to 7.0. The dye is with Salted out potassium chloride, filtered off with suction and with 25% potassium chloride solution washed. It is after addition of phosphate buffer at 50 ° C in vacuo dried.  

It corresponds to the formula

and dyes cotton in bluish red shades with an optimal dyeing temperature of 50 ° C and high fixation yield.
λ _max = 546 nm in water.

Example 78

78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are as described of Example 1 with 21.5 ml of cyanuric fluoride condensed.

It is allowed in 10 minutes, cooled to 0 to 3 ° C and Asked to pH 5 solution of 72 g

run in 250 ml of water while keeping the pH at 5.2 with 2N sodium carbonate solution.

The solution is prepared by sulfation of 2- (x-aminophenylethyl) -2-hydroxyethylsulfone according to the data of example 81.

69.7 g of 2-aminonaphthalene-1,5-disulfonic acid are dissolved in 500 ml of water Addition of sodium hydroxide solution to pH 7 dissolved. The solution is cooled and brought to 0 ° C, add it to 67.5 ml of 4N sodium nitrite solution and 300 g of ice and place in a Cast 60 ml of concentrated hydrochloric acid. After stirring for one hour is the diazotization  completed. It gives until the disappearance of the nitrite display amidosulfonic acid to.

In the submitted solution of the coupling component prepared above wear one the diazonium suspension at 0 ° C while maintaining the pH in Coupling mixture with dilute sodium carbonate solution to 7.0. After 3 hours you leave the Temperature rise to 20 ° C and salt after completion of the coupling the dye out. It is aspirated, washed and after adding some phosphate buffer dried. The dye of the formula

dyes cotton from long liquor at an optimum dyeing temperature of 50 ° C with good fixation yields in bluish red tones.
λ _max = 541 nm in water.

Example 79

• A. 500 g of styrene, 468 g of 2-mercaptoethanol, 5.0 g of azoisobutyronitrile are stirred, with the temperature rising to 30 to 33 ° C over approximately one hour. The mixture is stirred overnight and then heated to 50 ° C for 5 to 6 hours. The reaction is complete when a 1 H nuclear magnetic resonance spectrum no longer shows any of the characteristic styrene signals in the range δ = 4.80, 5.30 and 6.26 ppm.
  The resulting colorless liquid corresponds to the formula and still contains small amounts of 2-mercaptoethanol. The mixture is oxidized directly to the sulfone after dilution with 4.4 l of water (see Section C).
• B. The product obtained in A can also be obtained in the following manner:
  176 g of 2-chloroethylbenzene, 107 g of 2-mercaptoethanol, 198 g of potassium carbonate and 840 ml of acetonitrile are heated to reflux under stirring and nitrogen atmosphere at 86 ° C for 4 hours. After pouring into 8 l of water, the mixture is extracted by shaking with methylene chloride, the methylene chloride phase extracted with 2N sodium carbonate solution, washed with water and dried over sodium sulfate. After distilling off the methylene chloride in a rotary evaporator, finally in vacuo at 50 ° C, leaving behind a yellowish oil, which is identical to the thioether of Section A and shows the same signals in the ¹H-NMR spectrum. 1 H NMR (D₆-DMSO)
  δ = 2.60 ppm (t, 2H)
  δ = 2.73-2.83 ppm (m, 4H)
  δ = 3.53-3.60 ppm (m, 2H)
  δ = 4.78 ppm (t, 1H)
  δ = 7.20-7.30 ppm (m, 5H)
• C. The emulsion of 2-hydroxy-2'-phenyl-diethyl sulfide obtained in section 79A in 4.4 l of water is treated with 54 g of sodium acetate and 7 ml of glacial acetic acid to give a pH of 5.2.
  A solution of 7.9 g of tungstic acid in 120 ml of water and 5 ml of 50% sodium hydroxide solution is added, which was also adjusted to pH 5.2 with 7 ml of glacial acetic acid before addition. 932 g of 35% strength hydrogen peroxide are now allowed to run in at 55 to 60 ° C. in one hour, during which time a clear solution is formed, which becomes cloudy again towards the end of the addition. A chromatographic sample shows that sulfide is no longer present and essentially a mixture of the corresponding sulfoxide and sulfone is present. The oxidation to the sulfone is completed with a further 480 g of 35% hydrogen peroxide and subsequent stirring at 55 to 60 ° C. The batch is then cooled to 0 ° C. The crystallized sulfone is filtered off with suction and washed with several portions of ice-water. After drying, 920 g are obtained. The product melts at 56 to 59 ° C. 1 H NMR (D₆-DMSO)
  δ = 2.97-3.06 ppm (m, 2H)
  δ = 3.26 ppm (t, 2H)
  δ = 3.36-3.47 ppm (m, 2H)
  δ = 3.79-3.88 ppm (m, 2H)
  δ = 5.15 ppm (t, 1H)
  δ = 7.20-7.36 ppm (m, 5H)
• D. 135 g of the above sulfone 79C are added at 0 ° C in 445 ml of 96% sulfuric acid. As soon as a solution has formed, 120 g of mixed acid of 40 g of nitric acid and 80 g of sulfuric acid are added dropwise at -20 ° C. in 2 hours. The temperature is allowed to rise to room temperature overnight. The resulting mixture is poured into 1.5 kg of ice and 2.5 l of water and the resulting solution for saponification of the sulfato group for 4 hours at 106 ° C heated to reflux. The mixture is then cooled to 0 ° C. The compound of the formula crystallizes from the emulsion with stirring overnight or after seeding M.p .: 92-93 ° C 1 H-NMR (D₆-DMSO)
  δ = 3.12-3.22 ppm (m, 2H)
  δ = 3.28 ppm (t, 2H)
  δ = 3.47-3.53 ppm (m, 2H)
  δ = 3.90 ppm (t, 2H)
  δ = 4.74 ppm (1H wide)
  δ = 7.58 ppm (d, 2H)
  δ = 8.17 ppm (d, 2H)
• E. 200 g of 2- (4-nitrophenyl) ethyl-2'-hydroxyethylsulfone of Example 79D are catalytically reduced in 800 ml of methanol after addition of 10 g of Raney nickel at 60 ° C and 50 bar hydrogen pressure. It is diluted with 1 l of methanol, the nickel is clarified in the boiling heat and the filtrate is evaporated to dryness in a rotary evaporator. This gives 172 g of an oil, which solidifies on cooling to a crystal mass: M.p .: 58-62 ° C NMR (D₆-DMSO)
  δ = 2.88-2.96 ppm (m, 2H)
  δ = 3.19-3.34 ppm (t, m, 4H)
  δ = 3.74-3.81 ppm (m, 2H)
  δ = 5.03 ppm (s, 2H)
  δ = 5.13 ppm (t, 1H)
  δ = 6.52 ppm (d, 2H)
  δ = 6.92 ppm (d, 2H)
• F. 172 g of 2- (4-aminophenyl) ethyl-2'-hydroxyethylsulfone of Example 79E are introduced into 260 ml of 96% sulfuric acid at 0 ° C. Is then added dropwise at 0 ° C with cooling in 30 minutes 85 ml of 20% oleum and stirred for a further 2.5 hours with further cooling. The solution is added to 1.4 kg of ice-water, and the resulting precipitate is filtered off with suction and washed with 1.5 l of isopropanol free from sulfuric acid. After drying, a product is obtained which is of the formula has a content of 97.6% with respect to this formula. 1 H-NMR (D₆-DMSO)
  δ = 3.00-3.08 ppm (m, 2H)
  δ = 3.34-3.48 ppm (m, 4H)
  δ = 4.17 ppm (t, 2H)
  δ = 7.28 ppm (d, 2H)
  δ = 7.48 ppm (d, 2H)
  δ = approx. 9.7 ppm (wide)

Example 80

100 g of 2- (aminophenyl) -ethyl-2'-hydroxyethylsulfon be in a mixture of 147 ml of 20% oleum and 80 ml of 65% oleum at 10 to 15 ° C registered. When all is dissolved, add 80 ml of 65% oleum with cooling at 15 to 20 ° C and then the mixture is stirred for 17 hours at 25 ° C. A chromatographic Sample also shows complete sulfonation of the sulfonation after sulfation  aromatic ring. The approach is now carried out on 1.5 kg of ice so that the Temperature is maintained at 0 to 5 ° C. The resulting solution is at 0 to 5 ° C added with 460 g of calcium carbonate until a pH of 4.3 is reached. you sucks the calcium sulfate, washed with water and evaporated the combined Filtrates in a rotary evaporator in vacuo at 35 ° C to about 500 g of solution. The solution of the product of the formula is obtained

their content by titration with sodium nitrite solution in acidic medium with 0.324 moles = 99% of theory is found and used for the production of described dyes can be used directly.

A fully vacuum-evaporated and dried sample of this solution shows in a vacuum the following signals in the nuclear magnetic resonance spectrum:

1 H NMR (D₆-DMSO)
δ = 3.28-3.48 ppm (m, 6H)
δ = 4.13 ppm (t, 2H)
δ = 6.75 ppm (d, 1H)
δ = 7.20 ppm (d, 1H)
δ = 7.32 ppm (s, 1H)

Example 81

• A. 135 g of 2-hydroxy-2'-phenyl-diethylsulfone from Example 79C are introduced into 780 g of 90% sulfuric acid at 0 ° C. The mixture is then stirred for 30 minutes at 25 ° C until a clear solution is formed. 120 g of lactic acid are added dropwise at -13 to -7 ° C. in 4 to 5 hours from 40 g of nitric acid and 80 g of sulfuric acid, and the temperature is raised to about 0 ° C. overnight. The mixture is poured onto 2.7 kg of ice and 2 l of water and the mixture heated at 106 to 107 ° C for 4 hours under reflux. It is cooled to 0 ° C, sucked after stirring overnight, the somewhat soft crystalline mass and washed with 1500 ml of ice water acid-free. After vacuum drying at room temperature, 133 g of an isomeric mixture of melting range 69 to 83 ° C, which corresponds to the formulas and in which the p-isomer is predominant.
• B. 133 g of the nitro isomer mixture obtained above are reduced in 500 ml of methanol in an autoclave at 60 to 70 ° C and 60 bar hydrogen pressure in the presence of Raney nickel. After clarification of the solution diluted with 400 ml of methanol at 64 ° C, the resulting solution is evaporated. The remaining brownish oil crystallizes on standing. Are obtained 115 g of crystals, that of the formula corresponds and a melting interval 45 to 51 ° C.
• C. For sulfation, melt 100 g of the above Aminosulfonverbindung at 55 ° C and the melt is slowly added dropwise to 150 ml of 96% sulfuric acid, which is maintained at 25 ° C.
  When all is dissolved, cool to 0 ° C, add 50 ml of 20% oleum and stir for 15 hours at 0 to 5 ° C. The solution is poured onto 800 g of ice and 800 ml of water, neutralized with about 338 g of calcium carbonate to pH 5.2, freed by filtration of calcium sulfate, the calcium sulfate washed with water and the combined filtrates concentrated to about 600 ml. Obtained is a solution of the sulfato compound of the formula

Example 82

117 g of β- (4-nitrophenyl) -ethyl chloride are dissolved in 500 ml of ethanol at 67 g 2-mercaptoethanol and 124 g of potassium carbonate at 50 to 60 ° C heated. To After completion of the reaction, the ethanol is distilled off in vacuo, the remaining Oil washed with water and after emulsifying in 400 ml of water after the procedure of Example 79C oxidized with hydrogen peroxide to the sulfone.

Example 83

In analogy to Example 82, from 2-nitrophenylethanol (after a reaction with SOCl₂) by replacing the chlorine atom with the 2-mercaptoethanol radical and Oxidation of the recovered thioether with H₂O₂ the compound of formula receive,  

from which, after catalytic reduction of the nitro group and subsequent Esterification with sulfuric acid to make the following compound.

Example 84

In analogy to Example 79A, 49.7 g of 3-nitrostyrene, 31.5 g of 2-mercaptoethanol are added and 0.4 g azoisobutyronitrile together, stirring overnight and then heated to 50 ° C. The obtained compound of the formula

is oxidized with H₂O₂ in analogy to Example 79C to the sulfone, the nitro group catalytically reduced and the resulting amino compound with sulfuric acid to Sulfato compound of the formula

transformed.  

Example 85

According to the procedure of Example 76, 78.4 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 21.5 ml of cyanuric fluoride and 72 g of 2- (4-aminophenyl) -ethyl-2'-sulfatoethylsulfone a solution of the coupling component

manufactured.

39.8 g of 2-aminobenzenesulfonic acid are dissolved in 300 ml of water and 112 ml of 2N sodium hydroxide solution dissolved at pH 6. 57.5 ml of 4 N sodium nitrite solution are added. The The resulting solution is allowed in 30 minutes in a given mixture of 200 ml Water, 60 ml of concentrated hydrochloric acid and 2.5 ml of 4N sodium nitrite solution at 0 to 2 ° C run. The mixture is subsequently stirred for 1 hour, eliminating a little excess nitrous acid with sulfamic acid and contributes to the diazo suspension obtained 0 to 3 ° C in the above solution of the coupling component, wherein in the The resulting mixture by simultaneous addition of 2N soda solution pH value to 6.5 holds. After stirring for two hours with cooling, the Temperature rise to 20 ° C.

After completion of the coupling, the dye is salted out with sodium chloride, filtered off, washed with 25% sodium chloride solution and after buffering at Dried at 50 ° C in a vacuum.  

It corresponds to the formula

and dyes from long liquor at an optimum dyeing temperature of 50 ° C with good fixation yields in red shades.
λ _max = 532 nm in water.

Further dyes are synthesized analogously from the components specified in the following list.

Example 103

41.7 g of azo compound of the formula

in 800 ml of water by adjusting a pH of 4.5 with 2 n Sodium hydroxide dissolved. After cooling the solution to 0 ° C is added dropwise in 10 minutes 8.2 ml of cyanuric fluoride and the pH is maintained at 4.5 to 4.7 with 2N sodium carbonate solution. The mixture is stirred for 10 minutes and then sets a neutral solution of 39.4 g Component of the formula

in 150 ml of water, which is obtained according to the procedure of Example 80. During dosing, the temperature is kept at 0 to 2 ° C and the pH with sodium carbonate solution kept at 5.5 to 5.7. After 2 hours you leave the Temperature rise to 20 ° C. When the condensation is complete, the dye becomes salted out with potassium chloride, filtered off with 15% potassium chloride solution washed and after offsetting with a little phosphate buffer solution at 50 ° C in vacuo getrockent.

The dye of the formula  

dyes cotton from a long liquor with an optimal dyeing temperature of 50 ° C and high fixation yield in scarlet tones.
λ _max = 500 nm in water.

Example 104

24.5 g of azo compound of the formula

are dissolved in 340 ml of water at pH 7. After cooling to 0 to 2 ° C is set The pH value with dilute hydrochloric acid to 4.5 and then immediately leaves 4.3 ml of cyanuric fluoride drop in 4 minutes. The pH is further increased to 4.5 with 2N sodium carbonate solution held. 15 minutes later, the conversion is completed. A solution made up to pH 6 with 10% strength lithium hydroxide solution is then added of 18.6 g component of the formula

in 100 ml of water and keeps the pH in the reaction mixture to 5.0 to 5.5. After 2 hours, the temperature is allowed to rise to 20 ° C. Add 1 g of primary sodium phosphate, adjust the pH with dilute Sodium hydroxide solution to 5.5 and then evaporated the solution in a rotary evaporator at 35 to 40 ° C in a vacuum. This gives an orange powder, the cotton from a long liquor with an optimal dyeing temperature of 40 to 60 ° C and excellent fixation yield in reddish orange tones.

The resulting dye has the formula

λ _max = 497 nm in water.

Further orange-dyeing dyes are obtained by analogously condensing the following azo components with cyanuric fluoride and aminophenylalkyl-β-sulfatoethylsulfones.

Example 121

35.0 g of the coupling product of 2-aminonaphthalene-6,8-disulfonic acid 3-Aminoacetanilide in 600 ml of water at pH 5.5 with heating to 50 ° C. solved. It is cooled to 0 ° C and leaves 7.7 ml of cyanuric fluoride in 5 to 10 minutes dropwise. The pH is with dilute sodium carbonate solution to 5.2 to 5.5 held.

When the reaction is complete in about 10 to 15 minutes, one is allowed to pH 5.5% solution of 35.0 g of compound

in 120 ml of water is added dropwise and the pH is maintained with dilute sodium carbonate solution 5.5 to 5.7, the temperature at 0 to 5 ° C, later increasing to 15 to 20 ° C. The resulting solution, after addition of 1.5 g phosphate buffer of pH 6 im Vacuum at 35 to 40 ° C evaporated or spray dried.

The resulting dye of the formula

dyes cotton from long fleece with an optimum dyeing temperature of 50 ° C in golden shades.
λ _max = 389 nm in water.

Further reddish yellow-yellowing FFAs are obtained by condensation of the following p-aminoazo compounds with cyanuric fluoride and aminophenylalkyl-β-sulfatoethylsulfones.

Example 133

24.2 g of aminoazopyrazolone of the formula

(prepared by coupling diazotized 2-amino-4-formylamino-benzenesulfonic acid on 1- (4'-sulfophenyl) -3-carboxy-5-pyrazolone and saponification with dilute Sodium hydroxide solution) are dissolved in the form of the sodium salt in 600 ml of water. you Cools to 0 to 2 ° C, the pH with dilute hydrochloric acid to 5.0 and allowed Immediately add 4.0 ml of cyanuric fluoride within about 5 minutes. The pH is constantly kept between 4.3 and 4.6 by means of 2N soda solution. Is the Reaction is complete after 15 minutes, one with lithium hydroxide solution to pH 5.7% solution of 17.0 g of the compound of the formula

in 120 ml of water at 0 to 5 ° C was added. The pH is kept at 2 n Sodalösung to 5.5 to 6 and leaves after 2 hours, the temperature to 20 ° C rise.  

The resulting dye of the formula

dyes cotton from long fleet in greenish yellow tones with good Fixation.

Example 134

If, in Example 133, the 5-amino-2-sulfophenylazopyrazolone component is replaced by an equivalent amount of the corresponding 4-amino-2-sulfophenylazopyrazolone, This gives a dye of the formula

of cotton in reddish yellow tones as that of the example 133.

Other yellow dyes with similar properties are obtained by condensing the following Aminophenylazopyrazolone with cyanuric fluoride and the indicated Aminophenylalkyl-β-sulfatoethylsulfonen.

Example 142

19.9 g of azo compound of the formula

prepared by coupling diazotized 4-acetylamino-2-aminobenzenesulfonic acid to 1,4-dimethyl-6-hydroxy-5-aminocarbonyl-3-sulfomethylpyridone-2 and Saponification of the acetylamino group in dilute sodium hydroxide solution is carried out in 400 ml Water dissolved at pH 5.0.

After cooling to 0 ° C is allowed to run 4.1 ml of cyanuric fluoride and keeps the pH with 2N soda solution to 4.5. It is stirred for 15 minutes under the same Conditions and then sets a neutralized with lithium hydroxide solution of 15.7 g component of the formula  

in 110 ml of water. The pH is kept at 5.5 to 5.7 with sodium carbonate solution Temperature continues to 0 to 3 ° C and causes the condensation by stirring Night over. The dye is salted out with potassium chloride, filtered off with suction and washed with 15% potassium chloride solution.

It corresponds to the formula

λ _max = 422 nm in water
and dyes cotton from a long liquor with an optimum dyeing temperature of 40 to 50 ° C in brilliant greenish yellows.

Similar dyes are obtained by reacting the components of Examples 143 to 154 with each other according to the procedure of Example 142.

Example 155

A solution of 22.6 g of the component of the formula

in 60 ml of water, obtained according to the example of Example 80, is mixed with 2 g Sodium fluoride added and adjusted to pH 3.5. 5.2 ml is allowed at 0 ° C Cyanuric fluoride is added dropwise in 5 minutes and the pH is maintained at about 54 ml 2 n Soda solution at 3.5 to 3.7.

25 g of 1-amino-4- (2'-aminomethyl-4'-methyl-6'-sulfophenyl-amino) -anthraquinone-n- 2-sulfonic acid in 400 ml of water and 50 ml of acetone by neutralization with About 28 ml of 2N sodium hydroxide solution dissolved at pH 7. After cooling the solution to 0 to 5 ° C allowed to run the solution of the above reactive component and keeps the pH with 2N soda solution to 6.5. Upon completion of the condensation, the dye either salted out or isolated by running in vacuo at 35 to 40 ° C. He corresponds to the formula

Can be used for printing or dyeing by continuous cellulosic processes and provides clear reddish blue hues. Very good fixation yields are achieved (λ _max = 624 and 587 nm, in H₂O).

Example 156

14.7 g of 1-amino-4- (3'-amino-phenylamino) -anthraquinone-2,4'-disulfonic acid dissolved in 250 ml of water at pH 5 and 0 to 5 ° C. 2.8 ml of cyanuric fluoride are left within 5 to 10 minutes drops to the solution of the color component and holds adjust the pH to 4.2 to 4.7 with 2N sodium carbonate solution. After a short stirring is the Condensation to Difluortriazinylfarbstoff terminated.

A neutralized solution of 12.3 g of compound of the formula

in 40 ml of water now becomes the solution of the reactive dye component added slowly while maintaining the pH at 5.0 to 5.6. After that stops the pH to 6.0 and allowed in the course of 15 hours, the temperature gradually rise to 20 ° C, after which the condensation is completed. The Dye solution is now salted out within 2 hours. You suck that precipitated dye of the formula

λ _max = 604 nm (H₂O)
and wash it with saline until the light drain. After drying in vacuo at 45 ° C to obtain a product with the cellulose fabric in blue shades and can be dyed and printed with good Fixierausbeute.

Example 157

16.7 g component of the formula

are adjusted to a pH of 4.0 in 80 ml of water. It is 1.9 g Sodium fluoride to the solution and cooled to 0 to 2 ° C from. Then allowed 4.2 ml Cyanuric fluoride run under further cooling and keeps the pH with Soda solution between 4.0 and 4.2. About 15 minutes after cyanuric fluoride addition is the implementation completely finished. The solution is now adjusted to pH 4.5 to 5.0. The The reactive component obtained is neutralized in the course of 30 minutes Solution of 19.0 g of 1-amino-4- (3'-amino-2'-methyl-phenylamino) -anthraquinone 2,5'-disulfonic acid in 350 ml of water was added dropwise. One keeps in the reaction solution The temperature further to 0 to 5 ° C and the pH with sodium carbonate solution 6.0 to 6.5. After 2 hours, let the temperature within 15 hours gradually rise to 10 ° C. After completion of the condensation of the Dye of the formula

salted out of the solution with sodium chloride, filtered off with suction, with 20% strength Washed sodium chloride solution and dried at 45 ° C in a vacuum.

The dye gives on cotton blue dyeings and prints with good Fixation.

Other blue anthraquinone dyes with similar properties are obtained if one of the anthraquinone components of the general formula

condensed with the trihalo-triazines and the Sulfatoethylsulfonylalkyl-anilines according to one of the methods set out above.

Example 167

65 g of the sodium salt of the compound of the formula

are dissolved in 200 ml of water at pH 7.5. It is cooled to 0 ° C and leaves in 20 9 minutes of trifluorotriazine, while keeping the pH by adding of soda solution at 6 to 7. After completion of the reaction, a neutralized Solution of 18.3 g of the compound of the formula

in 80 ml of water, prepared according to the instructions of Example 6, added dropwise and the pH was kept at 7 with soda solution. After condensation is the Dye either by evaporation or spray drying or by salting out isolated. The dye of the formula thus obtained  

λ _max = 611 nm
dyes cotton in real blue tones.

Example 168

Another valuable dye is obtained by substituting for example 167 used color base, the sodium salt of the compound of formula

used and otherwise proceeds analogously. The dye of the formula thus obtained  

λ _max = 589 nm
dyes cotton in real blue tones.

Example 169

If in Example 91 instead of the isomer mixture 2- (x-aminophenyl) - ethyl-2'-sulfato-ethylsulfone equivalent amounts of 2- (2-aminophenyl) -2'- Sulfatoethylsulfon, then the dye of the formula

λ _max = 612 nm
the cotton according to the usual reactive dye application methods in blue shades.

Other formazan dyes in the following table can be obtained by Combination of appropriate components.

Table 1

Examples 176 to 183

Further dyes of the general formula according to the invention

can be analogous to the embodiment by implementing the in Table 2 produce specified components.  

The dyes obtained have very good fiber-reactive dye properties and provide by the usual dyeing and printing strong color true dyeings and prints with the color given in the respective table example on cotton.

Example 184

A neutralized solution of 14.4 g component of the formula

and 1.6 g of sodium fluoride in 60 ml of water is cooled to 0 to 2 ° C. One lets 5.5 g of cyanuric fluoride run in and keeps the pH between with 2 N sodium carbonate solution 3.5 to 4.0. After completion of the condensation, the pH is adjusted to 5.0.

32 g of copper phthalocyanine component of the formula

produced according to the specifications of European Patent 00 73 267, are in Dissolved 300 ml of water at p = 7.0 to 7.5. Now let the solution of the above Run the condensation product to the dye component at 0 to 5 ° C and keeps the pH in the reaction mixture at 7.0 to 7.5. After 3 hours leaves The temperature is gradually increased to 20 ° C and keeps the pH constant. After completion of the reaction, the product obtained from the solution salted out, filtered off with suction, buffered with a little phosphate solution at pH 6.0 and dissolved in Vacuum dried at 45 ° C. The dye corresponds to the formula

λ _max = 668 nm, 627 nm in H₂O.

The dye provides turquoise blue dyeings and prints on cellulosic fibers.  

Example 185

Substituting in Example 184 instead of the local 32 g Kupferphthalocyaninkomponente 32.4 g of copper phthalocyanine compound of the formula

(prepared by condensation of copper naphthalocyanine tetrasulfochloride / sulfonic acid with monoacetylethylenediamine and subsequent saponification according to the Information of German Patent Application 16 44 681, Example 2) and proceeds otherwise according to the information there, then you get a dye of formula

which provides turquoise blue dyeings and prints with good yield on cellulosic tissue.
λ _max = 668 nm, 628 nm in H₂O.

Example 186

31.2 g of copper phthalocyanine compound of the formula

prepared by condensation of copper naphthalocyanine tetrasulfochloride / sulfonic acid with 3-aminoacetanilide and ammonia and subsequent saponification of Acetylamino group in dilute sodium hydroxide solution at 75 ° C, in 420 ml of water dissolved at pH 7. 3.1 ml of cyanuric fluoride are added dropwise to the solution at 0-3 ° C and keeps the ph value at 4.5 to 5.0 with 2N soda solution. After finished Condensation is the solution of 11.5 g of reactive component of Example 6C in 50 ml of water are added and the condensation with the Difluortriazinylfarbstoff at pH 5.5 to 6, first at 0 to 5 ° C and later at room temperature rising to the end. The resulting dye of the formula

λ _max = 667 nm, 627 nm in water
is isolated by evaporation in vacuo or spray drying or by salting out, being buffered before the drying process with little phosphates to pH 6. The dyestuff dyes and prints cotton by the methods known for reactive dyestuffs, real and rich in turquoise shades.

Further phthalocyanine reactive dyes are obtained by condensing together the phthalocyanine components, trifluorotriazine and β-sulfatoethylsulfonylalkylanilines given in the following list, by one of the methods described above.

Example 200

36.7 g of prepared by known route amino-disazo compound of the formula

are dissolved in 400 ml of water at a pH of 6.0. After cooling the Solution to 0 ° C is allowed to rapidly dropwise 5.0 ml of cyanuric fluoride and keeps the pH with 2N soda solution to 4.5 to 5.0.

After completion of this first condensation stage carries 17.4 g isomer mixture from example 81C and keeps the pH with soda solution at 5.5 to 6.0. The mixture is stirred for 2 hours at 0 to 5 ° C and then left under further pH control the temperature rises to 20 ° C. The resulting dye of the formula

is salted out with sodium chloride, filtered with suction and after buffering at pH 6 im Vacuum dried at 45 ° C. He dyes cotton for the reactive dyes known methods yielding in brown tones.  

Example 201

Substituting the compound instead of the Aminodisazoverbindung of Example 200 the formula

condensed with cyanuric fluoride and then with the compound of formula

This gives a dye of the formula

The cotton also richly colored in brown tones.

Further brown reactive dyes are obtained by condensation of the following components.

Example 206

50.3 g of aminoazo compound of the formula

are dissolved in 400 ml of water at pH 6. The solution is cooled to 0 to 2 ° C from and drops 9.3 ml of cyanuric fluoride in a few minutes. During this Operation is maintained the pH with 2N sodium carbonate solution to 4.5 and then stirred the same conditions for a short time after. Is the soda consumption to Standstill, allowed one with 10% strength lithium hydroxide solution to pH 6 Asked solution of 32.3 g of 4 - [(2-sulfatoethylsulfonyl) ethyl] aniline in 180 ml Run in water and keeps the pH in the reaction mixture to 5.5 to 6.0. After 3 Hours are allowed to increase the temperature gradually to 20 ° C and isolated the obtained dye of the formula

by salting out and vacuuming. After gentle drying, a powder is obtained the cotton by the usual methods colors richly in scarlet tones.  

example 207

If the aminoazo compound is replaced by an equivalent amount in Example 206 the isomeric compound

condensed with cyanuric fluoride and in the second stage with the compound of formula

this gives the dye of the formula

the cotton colors in reddish orange tones with good fixation yields.

Further reactive dyes based on aminoazonaphthol compounds are obtained by condensation of the following components.

example 214

According to Example 184 condensed 19.5 g component of the formula

with 7.4 g of cyanuric fluoride in 80 ml of water in the presence of 2.1 g of sodium fluoride. The resulting solution of the condensation product is allowed to pH 7 Asked, 0 to 5 ° C cooled solution of 31 g of azo compound of the formula

Enter in 300 ml of water while keeping the pH in the mixture dilute sodium carbonate solution to 6.5. After 3 hours, the temperature gradually rises Increased to 20 ° C. After condensation, the dye is by salting out and vacuumed and after buffering to a pH of 6.5 in vacuo dried at 45 ° C. It corresponds to the formula

and dyes cotton from long fleet in bluish red tones with good Fixation.

Similar red dyes are obtained by reaction of the following components.

example 219

According to Example 184, 19.5 g of the component of Example 80 are dissolved in 80 ml of water and 2.1 g of sodium fluoride condensed with 7.5 g of cyanuric fluoride.

22.1 g Triphendioxazinverbindung the formula

are dissolved in 300 ml of water by addition of sodium hydroxide solution at pH 11.5-12.

This solution and that of the reactive components prepared above are now left simultaneously dripped into 80 ml of submitted ice-water and keeps in the reaction mixture Adjust the pH to 8-8.5 with 2N sodium hydroxide solution, keep the temperature 0-2 °. After several hours, the implementation is complete. The temperature is left rise to 20 ° overnight. The dye is salted out, filtered off with suction and after Buffering to pH 6.7 at 45 ° in a vacuum. It corresponds to the formula

and dyes cotton by the usual methods with good fixation yields in rich blues.

example 220

27 g triphioxazine compound of the formula

be in 1000 ml of water 12484 00070 552 001000280000000200012000285911237300040 0002004139319 00004 12365 with 10% lithium hydroxide by adjusting the pH to 7.0.

It is cooled to 0 to 5 ° C and added dropwise 5.3 ml of cyanuric fluoride. The pH in the reaction mixture is determined by dropwise addition of 10% strength lithium hydroxide solution kept at 6.0 to 6.5. To end the implementation increases keep the temperature within 2 hours at 20 ° C and keep the pH on in the above limits, until the consumption of neutralizing agent comes to a standstill comes.

Now, a neutralized solution of 18.5 g of component from Example 81C in Added 80 ml of water to the primary condensation product and the pH further kept at 6.0 to 6.5 with lithium hydroxide.  

The resulting dye of the formula

dyes cotton from a long liquor with an optimum dyeing temperature of 70 to 80 ° C in strong reddish blue tones.

Further triphendioxazine reactive dyes are prepared in an analogous procedure to Examples 219 and 220 by condensation of the following components:

example 226

35.2 of the known compound

are dissolved in 350 ml of water and the pH of the solution is adjusted to 5.0. you The solution is cooled to 0 ° C, 7.4 g of cyanuric fluoride is added dropwise and keeps the pH with 2N soda solution to 4.5.

After completion of the reaction, a neutralized solution of 17.0 g Component of Example 4F in 70 ml of water and keeps the pH with 2 n Sodalösung to 6.0, the temperature initially held for 4 hours 0 to 5 ° C. and then gradually increased to 20 ° C.

After condensation is complete, the dye becomes pH 6 after buffering either directly by spray drying or by salting out, vacuuming and Vacuum drying at 40 ° C isolated. The dye has the formula

and dyes cotton by the usual dyeing techniques for reactive dyes rich in navy blue tones.

Other similar cellulose fibers navy blue to black dyeing reactive dyes  are obtained if one of the following in the compilation listed Aminodisazo components of the general formula

condensed with the trihalo-triazines and β-sulfatoethylsulfonylalkylanilines.

example 238

50 mmole of the known copper complex compound of the formula

are dissolved in 600 ml of water at pH 6.5. It is cooled to 0-3 ° and allowed to Solution 7.4 g of cyanuric fluoride in a few minutes. During the dripping keep the pH with 2N soda solution at 4.5-5.0. After about 15 minutes Stirring is added to the primary condensate a neutralized solution of 17.0 g of the compound of the formula

in 80 ml of water and keeps the pH in the reaction mixture with sodium carbonate solution 5.0-6.0. When the consumption of soda gradually comes to a halt, you leave the Temperature rise to 20 °. After completion of the reaction, the dye of the formula

salted out, isolated and dried after buffering to ph 6 in vacuo at 45 °.

The product dyes cellulose fibers according to the usual for reactive dyes Color techniques with very good fixation yield in navy blue tones.

example 239

A neutralized solution of 24.7 g component of the formula

and 2.4 g of sodium fluoride in 100 ml of water is analogous to Example 99 with 8.6 g Cyanuric fluoride condenses.

The resulting solution is allowed at 0-2 ° C to a neutral solution of 50 mmols the known copper complex compound of the formula

Run and keep the pH in the reaction mixture with 2N sodium carbonate solution to 5-6. If the intake of soda subsides after a few hours, the temperature becomes slowly increased to 20 °.

After completion of the condensation of the dye of the formula  

salted out, isolated and dried at 45 ° in vacuo. He dyes cellulose fibers according to the color techniques customary for reactive dyes in blue shades.

Other reactive dyes which dye cotton in a very rich manner by the usual dyeing techniques are obtained by condensing the known copper complex compounds set forth below in Examples 238 or 239 with the trihalo-triazines and the β-sulfatoethylsulfonylalkylanilines.

example 250

50 mmol of the 1: 2 chromium complex of the formula

by coupling diazotized 5-nitro-2-aminophenol with 1-amino-8-hydroxynaphthalene 3,6-Disulfonic acid and subsequent conversion into the 1: 2 Cr complex can be obtained in 750 parts of water at pH 7 dissolved and mixed with a solution according to the instructions of Example 108 44.7 g of the component of Example 80 and 15.5 g of cyanuric fluoride was prepared and the connection

contains. The pH is kept at 6-6.5 and the temperature at 20-25 °. To completed condensation, the resulting reactive dye is salted out, filtered off with suction and, after buffering to pH 6.5, gently dried in vacuo.  

The resulting dark powder turns cotton into greenish gray tones colored.

Substituting one instead of the above-mentioned pure chromium complex one 1: 1 mixture of the chromium complex and the corresponding cobalt complex a, then a dye mixture is isolated, the cotton in neutral lightfast gray or black tones colors.

example 251

50 mmole of the co-complex of the formula

are dissolved in 800 parts by volume of water at pH 6 and the solution at 0-5 ° cooled. With vigorous stirring, 14.9 g of cyanuric fluoride are added dropwise and kept adjust the pH to 4.5-5.0 with 2N soda solution. After completion of the primary condensation add a neutral solution, which in 150 ml of water 21.4 g of the component

and 17.0 g of the component of the formula

contains. The pH is kept at 5.5-6.0 and after 2 hours the temperature is lowered rise to 20 °. When the condensation is completed, the resulting reactive dye salted out, filtered off with suction and dried at 45 ° in vacuo. The resulting powder dyes cotton by the usual techniques for reactive dyes lightfast shades of brown.

example 252

50 mmole triphendioxazine compound of the formula

are dissolved at pH 6 in 900 ml of water. 14.9 g are added to the solution at 0-3 ° Add cyanuric fluoride and keep the pH at 4.5-5.0 with 2N soda solution.

After stirring for a short time, a neutral solution of 42.8 g of component is added Example 80 in 160 ml of water to the primary condensation product and holds the pH to 6.0. After the condensation by gradually increasing the Temperature is completed up to 20 °, the dye of the formula

salted out, isolated and dried.

It dyes cellulose fibers in greenish blue tones.

example 253

21.9 g of 1- (4-benzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 250 ml of water dissolved at pH 5.5. After cooling the solution to 0-3 ° 7.1 g of cyanuric acid are added dropwise rapidly and the pH in the reaction mixture with dilute sodium carbonate solution kept at 4.5. After a short stirring, set one cooled to 0 ° neutral solution of 16.3 g component of Example 81C in 80 ml Add water and keep the pH at 5.5-6.0 overnight. After finished Condensation is added to a diazonium salt suspension, which is customary Obtained by diazotization of 8.7 g of 2-aminobenzenesulfonic acid, and The coupling is carried out by adding iodine at pH 6.5-7, first at 0 ° for several hours rising to 20 ° later. The resulting dye of the formula

is isolated and dried. He gives strong red cotton on long-handled cotton Colorations of good light and wet fastness.  

example 254

25.7 g of triazole of the formula

prepared according to the specifications of European Patent 00 13 879, be in pH 6.5 dissolved in 700 ml of water. It is cooled to 0 ° and slowly drips 6.9 g Cyanuric fluoride too. The pH is maintained with sodium bicarbonate solution 6.0-6.5. When the reaction is over after a few minutes, you put one neutral, cooled solution of 20.2 g component of Example 80 in 80 ml of water to and keeps the pH with sodium carbonate solution to 6.5.

After 2 hours, the temperature is allowed to rise to 20 °. It is mixed with 3.7 g Sodium nitrite and allowed to flow into 20 ml of 28% hydrochloric acid. After an hour of Afterreacting eventually becomes excess nitrous acid with sulfamic acid destroyed. Now 6.5 g of barbituric acid is added and coupled by adding Sodium acetate first at pH 5, later with soda at pH 5.5-6. After completion the coupling, the dye is isolated and dried at 40 ° in vacuo. He corresponds to the formula

and dyes cotton in brilliant yellows.

Similar yellow dyes are obtained by replacing barbituric acid the following coupling components are used:

2,6-dihydroxypyridine-4-carboxylic acid
1- (4-sulfophenyl) -3-methyl-pyrazolone (5)
1- (4-sulfophenyl) -pyrazolon- (5) -3-carboxylic acid
1,4-dimethyl-2-hydroxy-pyridone (6) -5-carboxamide
1,4-dimethyl-2-hydroxy-3-sulfomethylen-pyridone (6) -5-carboxamide
Acetoacetic acid-N- (2'-methoxy-5'-methyl-4'-sulfophenylamide)
Acetoacetic acid-N- (2 ', 5'-dimethoxy-4'-sulfophenylamide)
1-phenyl-3-methyl-5-aminopyrazole
1- (6,8-disulfonaphthyl- (2)) - 3-methyl-pyrazolone (5)
1,4-dimethyl-2-hydroxy-5-cyano-pyridone (6).

Further yellow dyes are obtained if, instead of the sulfatoethylsulfone Component of Example 80 uses that of Example 81C.  

example 255

To a dye solution, which was synthesized according to Example 76, one sets after 3.0 g of pyridine-3-carboxylic acid. The solution is warmed to 75 to 80 ° C and keeps the pH with 2N soda solution to 7.0 until the exchange of Fluorine atom is completed against the nicotinic acid residue. After cooling, the Salted out the dye or the solution after desalting and concentrating as Liquid dye can be used.

The dye corresponds to the formula

and dyes cotton from a long liquor similar to the dye of Example 76.

Similarly, the others in the previous examples described fluorotriazine dyes in the 3-carboxypyridinium triazine dyes being transformed.

Claims (14)

1. reactive dyes of the formula wherein
D = residual organic dye,
B = direct bond or bridge member to a ring C atom of an aromatic carbocyclic or to a ring C atom or N atom of an aromatic heterocyclic ring in D,
R _a , R _b = identical or different, H, C₁-C₄-alkyl or with OH, CN, CO₂H, OSO₃H or SO₃H substituted C₁-C₄-alkyl,
U = Cl, F or an optionally substituted by CO₂H, CONH₂, SO₃H or C₁-C₄-alkyl pyridinium,
W = straight-chain or branched C₁-C₆-alkylene,
Y = CH = CH₂ or CH₂-CH₂-X, wherein
X = alkaline eliminable radical,
V = H, halogen, C₁-C₄-alkoxy, C₁-C₃-alkyl, CN, COOH, CONH₂
with the proviso that

• a) D = the radical of a dye of the formazan, phthalocyanine, anthraquinone and triphendioxazine series, when W = -CH₂-, and
• b) D = radical of a dye of the formazan, phthalocyanine, anthraquinone and triphendioxazine series or
  U = F or an optionally substituted by CO₂H, CONH₂, SO₃H or C₁-C₄-alkyl pyridinium,

when the radical W is C₂-alkylene. 2. A reactive dye according to claim 1, wherein mean
D = remainder of a dye of the formazan, phthalocyanine, anthraquinone and triphendioxazine series,
W = C₁-C₄-alkylene. 3. A reactive dye according to claim 1, wherein mean
W = C₂-C₆-alkylene,
U = F or a pyridinium radical which may be substituted by CO₂H, CONH₂, SO₃H or C₁-C₄-alkyl. 4. Dyestuffs according to at least one of the preceding claims, characterized in that
X = OSO₃H, SSO₃H, OCOCH₃, OPO₃H₂, OSO₂CH₃, SCN, NHSO₂CH₃, Cl, F, Br, OCOC₆H₅, OSO₂-C₆H₄CH₃, N⊕ (CH₃) ₃. 5. A dye according to any one of the preceding claims, wherein
R _a = H or C₁-C₂-alkyl,
R _{b is} H, C₁-C₃-alkyl, β-hydroxyethyl, β-sulfatoethyl, β-carboxyethyl, β-cyanoethyl or carboxymethyl, Y = CH = CH₂ or CH₂-CH₂-X-, with
X = Cl or OSO₃H,
V = H, chlorine, C₁-C₂-alkyl, COOH, SO₃H, C₁-C₂-alkoxy. 6. Dyestuffs according to at least one of the preceding claims, characterized in that they correspond to at least one of the following formulas wherein
R _a = H or C₁-C₂-alkyl
Pc = phthalocyanine nucleus,
Me = divalent metal ion,
n = 0 or 1
u + v + w = 3-4, with the proviso that
w = 0.8 to 2.0
v = 0 to 1.0
u = 1.0 to 3.0,
A₁ = aliphatic, araliphatic or aromatic bridge member,
G = oxygen or -N-R₁₁, wherein
R₁₁ = H, C₁-C₂-alkyl, wherein when A₁ = C₂-alkylene, R₁₁ and R _a may be closed to a ring
T₁, T₂ = H, chlorine, bromine C₁-C₄-alkyl, C₁-C₄-alkoxy or acylamino,
R₁-R₆ = independently of one another H, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxy, halogen, carboxy, sulfonamido, alkyl- or arylcarbonylamine, or -sulfonylamino, β-sulfatoethylsulfonyl or SO₃H, carboxymethyl, carboxyethyl,
R₇-R₁₀ = H, C₁-C₂-alkyl, optionally substituted by hydroxy, carboxy or sulfonyl, wherein R₉ and R₁₀ may also be closed to form a ring, when A₁ = C₂-alkylene,
Z = a radical of the formula wherein U has the meaning given in claim 1,
A = a radical of the formula wherein W, V and Y are as defined in claim 5,
R₆ = H, C₂H₅, i-C₃H₇, n-C₃H₇, C₂H₄OH, carboxymethyl or carboxyethyl. 7. Dyestuffs according to at least one of the preceding claims, characterized in that they correspond to the following formula in which mean
U = F, Cl or an optionally substituted by COOH, CO₂NH₂, SO₃H or C₁-C₄-alkyl pyridinium, wherein V, W and R₆ have the meaning given in claim 6. 8. Amines of the formula wherein M = C₂H₅, C₃H₇, C₂H₅OH,
V¹ = H, Cl, SO₃H, CH₃, CO₂H, OCH₃,
L = CH = CH₂, CH₂-CH₂-Q,
Q = Cl, OH, -OSO₃H, 9. A process for the preparation of dyes according to at least one of the preceding claims, characterized in that a dye base of the general formula in which D, B, R _{a have} the meaning given in claim 1 is reacted with 2,4,6-trichloro- or 2,4,6-trifluorotriazine, the resulting intermediate in a further reaction step with an aminosulfone of the formula is implemented, or that you have a color base condensed with a fiber-reactive compound of formula (19) wherein the substituents have the meaning given in claims 1 and 5. 10. A process for preparing amines according to claim 8, characterized in that compounds of the formula (33) wherein
V¹, W¹ = as defined in claim 8,
E = NO₂ or acylamino,
Y¹ = Cl, Br or -OSO₃H
with 2-mercaptoethanol to sulfides of the formula (34) be reacted and these sulfones of the formula (35) wherein
Q¹ = HO or Cl,
are oxidized and then the nitro group E is reduced or the acylamino E saponified, the resulting amino compounds are N-alkylated, optionally then the OH group in Q¹ in a -OSO₃H group is converted and optionally the resulting amines by treatment with alkaline acting agents are converted into compounds of formula (32), wherein L is the -CH = CH₂ group. 11. A process for the preparation of amines according to claim 8 (with W = C₂H₄), characterized in that one of ethenylaromatics of the formula (33a) wherein
E¹ = H, NO₂ or acylamino, and
V¹ has the meaning given under formula (33),
2-mercaptoethanol to sulfides of formula (34a) radically catalysed added,
these to sulfones of the formula (35a) wherein
Q¹ has the meaning given in claim 10, oxidized and then, when E¹ = H nitrated to E¹ = NO₂, the nitro group E¹ reduced or the acylamino E¹ saponified, optionally the resulting amino compounds N-alkylated and / or the OH group Q¹ in converts an OSO₃H group and optionally in the phenyl nucleus in place of V¹ = H introduces a SO₃H group. 12. A process for dyeing cellulose and / or polyamide-containing materials with a reactive dye, characterized in that a reactive dye used according to at least one of the preceding claims becomes. 13. The method according to claim 12, characterized in that the dye in Blending with other dyes is used for trichromatic use.