DE1769370B2 - METHOD FOR MANUFACTURING REACTIVE DYES - Google Patents

Description

NC-Y-f ^ = - "X".

The invention thus provides a process for the preparation of reactive dyes in general Formula I.

10

• Ν-.

D-CH ₁ NH-CY- + -T- (Xl _n (Il

IN

in D the residue of an amidomethylatable anthraquinone derivative. X is a chlorine or bromine atom. Y denotes a single bond, a methylene _{or - CH 1} - CH ₂ - NH group and n denotes a number from 1 to 3, which is characterized by this. that 1 mol of an anthraquinone derivative containing substitutable hydrogen atoms in sulfuric acid or phosphoric acid with 1 to 3 mol of formaldehyde or a dihalomethyl ether and with 1 to 3 mol of a compound of the general formula II

NC Y

-4 f

^! N

in which X and η are as defined above and Y is a single bond or a divalent organic group. reacted and optionally converted the product obtained into a water-soluble alkali metal salt.

2. Use of the reactive dyes prepared according to claim 1 of those specified in claim 1 General formula for dyeing cellulose or nitrogen-containing fibers Textile goods.

Chlorpyrimidyl groups are known as reactive groups of reactive dyes (cf. Heinrich ZoI linger, Applied Chemistry. Vol. 73, p. 128 [1961]). These reactive groups are created by acylation Introduced in dyes containing amino groups: so it is difficult to identify the reactive group in dyes to introduce that do not contain amino groups.

It has now been found that by using chloropyrimidine derivatives with nitrile groups in accordance with the amidomethylation reaction, chloropyrimidyl groups can be introduced into anthraquinone derivatives, and reactive dyes which are distinguished from the known reactive dyes, for example by their hue and fastness, can be obtained, and that it is not always necessary is. that the anthraquinone derivative contains amino groups. The dyes obtained in this way belong to the so-called high-temperature fixing reactive dyes. and thus have dyed fibers e- an extraordinarily large sow and AU'.alibeständigkeil and authenticity compared with ai Tieltemperatur-Fixierfarbstoffen. such as B. dichlorotriazine or vinyl sulfone dyes, colored fsisers.

40

45 in which X. Y and π have the above definition, is reacted and, if necessary, the product obtained is converted into a water-soluble alkali metal salt.

From anthraquinone derivative with subsiiiübaren hydrogen atoms amidomethylatable anthraquinone derivatives are used. This anthraquinone diva can be divided into those who have the substitutable Wasierstoffatome on the aryl ring and in those that have the substitutable hydrogen atoms in Have sulfamyl groups.

The usual acidic anthraquinone derivatives with substitutable hydrogen atoms on the aryl nucleus are used. Dyes or dye bases used, ζ. Β Anthraquinone derivatives with —Nri-, - O-. - S-. - NH-alkylene, —O-alkylene, —S-alkylene and —SO ₂ NH groups. In this case, the aryl nuclei, in addition to the substitutable hydrogen atoms, preferably carry ο-, p-orienting groups, such as methyl and methoxy groups. The anthraquinone nuclei can be formed by hydroxyl. Amino, acetylamino or sulfo groups be substituted.

Dye base, iie from anthraquinones

vaten with substitutable hydrogen atoms in SuIf amyl groups are generally fü acidic dyes and disperse dyes used The sulfamyl groups with substitutable water Atoms of matter can be attached to aryl rings of arylamino, aralkylamine ode directly on the anthraquinone ring pod Aryloxy groups bound sHn, which in turn are bound to the An thrachinonring.

Most of the links are general! Formula II are known and can be used according to known! Processes from the chlorinated derivatives correspond to the pyrimidines by introducing nitrile groups ments or made from corresponding carboxamides.

Examples of preferred compounds of F01 m ° l II are 5-cyano-2,4,6-trichloropyrimidine, 5-cyar 2.4,6-tribromopyrimidine. 6-cyano-2,4-dichloropyrimidii 5 - cyano - 4 - chlorpyrimdin, 4 - cyano - 2 - chlorpyrirnidti 6-cyano methyl-2,4-dichloropyrimidine and 6 - (,; - cyar ethylamino) -2.4 ~ dichloropyrimidine.

According to the invention, compounds of the ileine formula Ii with the aforementioned anthraquinone substances - hereinafter referred to as fur base bodies - are converted into sulfuric acid or phosphoric acid in the presence of formaldehyde or Dilaioiienmethyla'iher. Thus, substituted atoms are substituted on aromatic rings or in sulfamic groups, whereby the reactive dyes of the general formula I are easily obtained according to the amidomial reaction. It is believed. tiaLi the <e reaction via the hydrosis of the NUr;! - jruppen in the compounds of the general form! And 11, the formation of methylol or hakiienmethvlienen derivatives verläu ^f i. ! The same Per ^\: e can also be obtained when> the \>; ■ · .. 'uni i after hydrolysis of Nurtlviruppen i Jen Xc' boys de general formula 1! / u c'arba. -: uppen performs.

\). The method according to the invention is followed by the _ril . ■■■ :. carried out: In sulfur or Phösphor-5,:. -. ·. Usually 85 to 100% sulfuric acid. Sj- · \ :, Λ'Λ per mole of the staining base! h-.s? v. ' a compound of the general formula II cn. short time at 0 to 20 Γ with as many moles {■ '. ·:.: \ i'deh \ d or a compound like Fo'miik !. ^; > d can react. e.g. Parafornia! deh_ \ d or DiLi'genmnethylather. around. The Sehwefels.iurc-Reaktj, .mi - .: e: iisch then wire the Farhstoffgrundko ^r .: i-- \ replaced and a k'jr / c / rc it at 0 to 20 (: -.-- older One can do the l'mset / unü aucli so du-J ^:! ". that one dissolves the dye: round body and the compound of the general formula 11 in S5- bis ', ("' i iger sulfuric acid and da / u ^r ^ rrr>al.iet;> d or a compound gi'.it. which can react like form- -.ri.ie! nd.

'■ -. • Before the end of the implementation, the reac-I is; :; - Mixture poured into fish water and then with ._ ·; ■: ·. m inorganic salt. e.g. sodium chloride or K.ii.unichlorid. salted out, whereby the Reaktic.nspr. ..iiikt received as precipitation. Nö'igenfails will o .- '. M. if the dyestuff thus obtained is difficult to dissolve in water, the dyestuff is also subjected to sulfonation in fuming sulfuric acid

With the reactive dyes of the invention, fibrous materials can be dyed firmly and in various ways au-deeply drawn real stains received.

Examples of fibrous materials that deal with the reactive fibers of the invention are dyed cellulose fibers. like cotton. Linen, viscose silk and viscose staple fibers, and nitrogen-containing fibers such as wool. Silk and polyamides. The reactive dyes of the invention can be used in many common dyeing processes, for example in the fuchsia, in the printing and in the toilet process.

Cellulose fibers are dyed in the dipping process at 80 to 100 C in a liquor which, in addition to uricrn acidic binders, such as sodium hydrogen carbonate. Sodium. Sodium hydroxide or tertiary Sodium phosphate, an inorganic salt such as sodium chloride or anhydrous sodium sulfate.

With the K'.otzdärbeverfahren you plop a raser with it a solution obtained by dissolving a reactive dye is made in urea-containing water. treats it "ntwedcr during the logging process or afterwards with an aqueous solution of an acidic binder, such as sodium hydrogen carbonate, Na- ! -. imcarbonate. Sodium hydroxide or tertiary sodium phosphate, and then steam or heat the fiber for a short time.

For printing, either a printing paste is used, which can, for example, be displaced an alkyl cellulose or sodium alginate paste with the reactive dye and the aforementioned acidic Has made binder. prints the fiber with this. Printing paste and then treating it with steam or heat, or you can use one to print on

ic fiber is a printing paste that is not an acidic binder contains, treats the printed fiber with the .orc name acidic binder and then steam ouer heat.

The dyeing of nitrogen-containing fibers is carried out as usual in a neutral or slightly acidic liquor. Included it is desirable that the liquor be a nitrogenous one nonionic or cationic surfactant as Fgalisierhilfsniitiel revealed and after completion of the Färber's neutralization treatment with weaknesses Alkali, such as hexamethylenetefamine. subject will

After dyeing, it is desirable that the dyed fiber be subjected to a soap treatment, to excess to remove sigen dye.

:> The fibers dyed in this way have an excellent Fastness to washing

The examples illustrate the invention. Parts are by weight.

example 1

4.6 parts of sodium 1 -amino-4- (2'.4'.t> -trimethylphenylamino) -anthraquinone- 2- sulfonate were hurried in 46 liters. 98 "sulfuric acid dissolved. 2.1 parts of 5-cyano-2,4-6-trichloropyrimidine were added to this solution at 10 ° C. or at lower temperature. After adding 0.3 part of paiüformaldehyde to the reaction mixture, the reaction was carried out at 10 ° C. for 1 hour The reaction mixture was poured into ice water, the precipitate formed was filtered off and washed with a 5% aqueous sodium chloride solution. After drying, the dye obtained was added at 10 ° C. to 46 parts of sulfuric acid containing 20 ° 0 sulfur trioxide; d.is mixture was stirred for 1 hour

and then poured into ice water containing 10% sodium chloride contained. A precipitate formed. which was filtered off and still moist in 15% aqueous Sodium chloride solution was suspended. After neutralization with sodium carbonate, the suspension became filtered to obtain a reddish blue dye with the following structural formula:

O NH,

O NH

H ₃ C SO ₃ Na

Example 2

4.3 parts of sodium 1,4-diamino-2-phenoxyanthraquinone - 3 - sulfonate were 90% strength in 43 parts

Dissolved sulfuric acid. This solution was with 1.9 parts of ö-cyanomethyl-I. ^ Dichloropyrimidine at 10 C or delivery temperature offset. 0.3 part of paraformaldehyde was added and the mixture was left for 2 hours react. The reaction mixture then became sulfuric acid containing 60 ° ο sulfur trioxide with cooling dropped to adjust the sulfur trioxide content of the liquid to 3 to 5%. After an hour While stirring, the reaction mixture was poured into ice water which contained 10 °. O sodium chloride. It a precipitate formed. which is discharged and still moist in a 15% strength aqueous sodium chloride solution was suspended. After neutralization with sodium carbonate, the suspension was nitrated and a bluish-purple dye of the following structural formula was obtained.

Cl

O NH ₁ -χ

NN CH ₂ NHCOCH ₂ Λ, ...-. \

Cl

SO ₃ Na

example

Dye base

Weight parts

2.3

2.5

Color tint

reddish blue

purple

! .4-bis (2'.4'.6-tri-

methylamino) -an-

thraciiinon

l-amino-2- (4-tert -

butylphenoxy

4- (2 ', 4', 6'-trimethyl-

phenylamino) -an-

thrachinone

Examples 5 and 6

1.8 parts of o-cyano-Z ^ dichloropyrimidine were dissolved in 51 parts of 9S% sulfuric acid at 10 ° C. or lower. This solution was admixed with 0.3 part of paraformaldehyde and stirred for 1 hour The dye base mentioned below was dissolved. The solution was allowed to react at 10 ° C. for 1 hour. The reaction mixture was then poured into ice water containing 5% sodium chloride. A precipitate fell out, which was filtered off and suspended while still moist in a 10% strength aqueous sodium chloride solution. After neutralization with sodium carbonate, the suspension was filtered. There were dyes
keep.

Example
No

with the specified color shades

SO ₃ Na

Examples 3 and 4

Example 1 was repeated, but instead of 4.6 parts of sodium 1-amino-4- (4 ', 4'.6'-trimethylphenylamino) anthraquinone-2-sulfonate the dye bases listed below are used, with Dyes with the specified shades were obtained.

6o dye base

I-C clohexylamino-J, 2.4'.6'-trimethylphenylamino) anthraquinone-6-sulfonic acid

l-amino-4- (3'-sulfamylphenylaminoh
anthraquinone-2-sulfonic acid

4.5

Color tint

blue

reddish blue

Examples 7 to 9

Example 2 was repeated, except that 4.3 parts of sodium 1,4-diamino-2-phenov were used anthraquinone-3-sulfonate the following dye base used. There were dyes m Sen prestigious shades received.

Example

No.

35

₄₀ dyes round body

; -phenyl-propyl-

amino ~) -anthra-

chinone

1.4-dianiino-2,3-bis-

phenoxyanthra-

chinone

1.4-bis- [4- (4 "-me-

thylphenoxy) -phe-

nylamino] -anthra-

chinone

Weight parts

3.0

\ ^: .irbti'nui '.

blue

reddish purple

bluish criin

Example 10

') NH,

Cl

CH ₇ NHCO - ^J :

.N-

Cl

Part of the dye of the above formula was dissolved 5 (X) parts of water. This solution was added to parts of anhydrous sodium sulfate. 20 parts of cotton were added to the mixture, and the temperature was raised to 50 ° to 90 ° C. Then v, adds the further 5 parts of sodium tertiary phosphate hinzt, and the cotton was dyed I hour, thus dyed cotton was subjected to Seifenbehandl · obtained washed mil water and so a farbi and clear reddish blue colored product.

769

O NH,

example

C H, NHCOCH, CH.NH

(SO ₃ Na) ₁₀ ,

Cl,

Cl

I, ·, 2

2 Toile of the dye of the above formula and 8 parts of urea were dissolved in 40 parts of hot water. 50 parts of a 5% sodium alginate containing This solution was added to paste while stirring. After cooling were added to the mixture Added 2 parts of sodium hydrogen carbonate. A cotton cloth was made with the printing paste thus obtained printed, dried and then treated with steam. Then the cotton cloth was given a soap treatment subjected, washed with water and so obtained a product that is sunlight and washfast and was clearly bluish purple in color.

Examples 12-18

It is colored as in Examples 10 and II Dyes, of the formula below, are obtained colored products with the listed colors:

example Structural formula

O NH ₂

CH ₂ NHCO (SO ₃ Na) ₂ ^ ₁

O NH ₂

O NH ₂

SO ₃ Na

CH ₂ NHCOCH ₂ CH ₂ O

O NH ₂

SO ₃ Na

H ₃ C

O NH

CH ₂ NHCO- (SO ₃ Na) ₂ -NH

Color tint

Reddish purple

Bluish purple

Rötlid blue

305 525

OrtNiM / uni!

Example i

No. i

Slruklurfi -mel

1 .tr h

NaQ ₃ S

CU,
O NH-CHCH ₂ CH ₂ - ^

O NH-CHCH ₂ CH ₂ - /
CH ₃

(SO ₃ Na) ₂

Cl

blue

blue

Greenish blue

Bluish green

From US Pat. No. 3,301,843, reactive 55 form soluble alkali metal or ammonium salts

1 j.er- J —II »« am I7a «- * v» & 1 CqiiM »» 4A * «» A # "·« -U 1 TM ■ - _ J _- O.

dyes of the general formula

X.-D

N-C

y \

- N - CO - C N

H (R) _4- , C = C

H Y acid residues, such as carboxyl, phosphoric acid or S fonsäuregnippen mean, D a pigment no külrest such as an azo, anthraquinone or phtha cyanine dye residue, R a divalent lower egg

aliphatic radical such as methylene, ethylene o <propylene group and Y is a fluorine or chlorate, π is an integer with a value of m at least 2, preferably 2 or 3, and m and q ύ have the value 1 or 2.

The one described in Example 6 of this patent specification « representative dye (A) is the anthraquinone dye prepared according to the invention according to the example

known in which X the same or different water (B) in the table below compared

11th

Q-,

dye

O NH

(A)

CH ₂ NHCO
CH ₃ Cl

H ₃ C SO ₃ H

The dye (A) is obtained by acylation of

O NH ₂ SQ ₃ H

12th

production method

Acylation

Amidomethylation

with an acid chloride of the formula

manufactured.

According to the invention, the dye (B) is prepared according to the following reaction scheme:

O NH

1. H ₂ SO ₄
NaCl

Y Ύ ³ \ z

H I V- /

O NH f > -

hue

blue

Bright reddish blue

The dyestuff produced according to the invention is your known dyestuff (Λ) in terms of its hue considerably superior.

From the Belgian patent 661 532 reactive dyes are known, inter alia, which are used as dye base bodies contain an anthraquinone derivative. The dye (C) described in Example 3 of this patent specification is compared to an anthraquinone dye (D) that can be prepared according to the invention in the table below:

Color stump (C)

O NH

SO ₃ Na CH ₃

CH ₂ NHCOCH ₂ SO ₂ CH ₂ CH ₂ OSO ₃ Na dye (D)

O NH

H ₃ C CH ₂ NHCO

Beneficial effect of the dyelot cotton Color change Fastness to washing Wool Construction roll Staining dye Wool (Alkali treatment) 5 Color change 5 some
inferior
50% 5 5 5 C. excellent
86% excellent
70% 5 D. excellent
86% Staining 3 to 4 3 to 4

The tests were carried out according to the Japanese industrial standard JIS L 1045 (1959). The dye according to the invention is the one from which it can be absorbed onto cotton Belgian patent 661 532 known dye superior.

Claims (1)

i 769 370 Patent claims: I. Process for the preparation of reactive dyes of the general formula D-CH ₂ NH-CY- ¹ - ^ r- (Xl _n in D the residue of an amidomethylatable anthraquinone derivative. X is a chlorine or bromine atom. Y is a single bond, a methylene or --CH ₂ - CH ₂ - NH group and r. denotes a number from 1 to 3, characterized in that 1 mole of an anthraquinone derivative containing substitutable hydrogen atoms in sulfuric acid or phosphoric acid with 1 to 3 moles of formaldehyde or a dihalomethyl ether and 1 to 3 moles of a compound of the general formula