DE1644367C - Process for the production of reactive dyes - Google Patents

Description

The invention relates to processes for the preparation of valuable reactive dyes of the formula

HOjS-O-A-0

NH-X

in which A is an alkyl ring with 2 to 3 carbon atoms, optionally carrying a hydroxyl group, X is at least one substituent unscleavable as an anion and / or a radical containing multiple bonds for addition, and Z is hydrogen, chlorine, bromine, low molecular weight alkyl or COOH.

The process for the preparation of the new reactive dyes is characterized in that 1 mol 2-Ainino-5-hydroxynaphthalene-7-silfonic acid in any Reacts sequence with at least 1 mole of an acylating agent, which after the reaction also at least one substituent which can be split off as an anion and / or a multiple bond capable of addition contains, and with 1 mole of the Diazovei bond from an amine of the formula

Y - O - A - O -

where Y is hydrogen or - SOjH, in the ortho position to the hydroxyl group and, when Y is hydrogen, with a sulfating agent treated.

A modification of this procedure is characterized in that there is 1 mole of the dia / oval bond from an amine of the formula (U) with 1 mol of 2-acylamino-5-hydroxynaphthalene-7-sulfonic acid, which Cleaves acyl group and reacts the amino group with at least 1 mol of an acylating agent which after the reaction, at least one substituent that can be split off as an anion and / or one contains multiple bond capable of addition and, when Y is hydrogen, the dye in any Stage of replacement of the acyl group by the remainder of X treated with a silicone fluid.

Suitable groups Y O V where Y is hydrogen> t, siiul / M .:

no cn, (ii,

HO CH, (Il t II.
HO CH, (H.

HO (Il

(II, cn. Ίο leads and, if Y is hydrogen, sulfates the dye or

b) first executes the coupling, then the reactive grate X introduces and, if Y is hydrogen, the dye before or after the introduction of the Most reactive residue X sulfated.

According to the second Ausfülmingsl'orm of the process / .. B. proceed so that when Y stands for hydrogen.

a) carries out the coupling, splits off the ayl group, the amino group with the reactive component

converts and sulfated the dye or

b) carries out the coupling, splits off the acyl group, sulfates the dye and the amino group with the reaction component converts or

c) carries out the coupling, sulfates the dye, splits off the acyl group and the amino group reacts with the reactive component or, if the Y door is the SO, H group, NH, (II) d) performs the coupling, splitting off the acyl group

and the amino group with the reactive component uinset / t.

The radical \, which has at least one substituent which can be split off as an anion. preferably a chlorine or bronuitoma or a Siilfatogi group O SO ₁ H

and / or a C C-Mehifachhinduni 'capable of addition, preferably one bound to a carbonyl or ^ uIiOIi) IuIuppe, optionally suh. stituierte ^: \ thvlengruppe reveals, is /. B. an aliphatic or heterocyclic acyl radical, which is voi

can derive from the following columns: chloressic acid Bromoacetic acid. ,; Chlorine and, ·> '■ Hromprop "· !!' · acid n./i'- dichloro- or. (,, .'- DihronipropiunsäiirL, Aci> l acid. -i-chlorine- and -i-brothic acrylic acid. << ,,; - and / ί ,, ί-Di chloro- or dibromoacrylic acid; -Chlor- and; -Bromine

crotonic acid, Ath \ lensulfousäurc, / ί-Chlor- odei / f - Bromäthaiisiilliiiisäiirc. ₍ f - sulfatopropioiisäure / i-sulfatoäthaiisiilfoiisäiire, 2.4-1> chloro- or 2.4-1> i bromopyriinidiii> - carboxylic acid. 2,4-1) chloro- odei 2,4-r) ibromo-f) -ineth> l, -d-chloromiethyl- or -d-di

ehlormetlnlpvriniidin - ^ -laibonic acid. 2. Ϊ -1) iehloi oilef 2.3-1) ibidinehino \ ahii - (> earboiisauie, - () - sullt> ii acid or (ι-earbaiiiin - .. iiiie; he can also express contains halogens ·! · heleroe.velisehei reads his. /. B en 4 i) Dichlui iulei -t.ii i) ibruin I. ' > -iria / iii) l-2-ie-.

si ('the one remainder of the I uiinel

ι iiler

IK) (Il ill (Il
Oll

N ₁ Il "Il dei 1'1" -. UNI \ \: .ίίΐΙΐΓΙ1ΙΙ: '-. | Ι μ ΊΙ {.'.

you can /. Ii. -; i ·, ;; i laliren -i.ili kmü
a) /ικί-.ι '.lie I-'. ii | i | iliiii! .'-- k (iiii; - 'i | r. ni.

livkliilll »ün'llll MlIl ¹ AI / !. iL'illll ill. ί

V ei lahu η-. '<■■ ·· ■ ui in I IaI (lilm uiKi ΙΙΐι, ηι and \ i \> ji \ ; · ^; \ Ί) οιυιιΙ, ιΙΙ

. ·. .Hei aiii I il κι ι u: ι Ue .1. Hh-. pi iinäieii or \ eknii

: ilei I · '. ik them ahpli.iii λ In n. aliev. II ··. ilen, al oinaliseheii ode

lietei 'u

.. hell Λίπΐιι, never!

'lialisi lien ude

aromatic hydroxyl pre-bond, especially itbur don rust from aniline, dosson alkyl and sulfonslluru ·· odor carboxylic acid derivatives, from low mono- and dialkylaminon and the remainder of ammonia or also a dihalogen or trihalogenpyrimidyl radical or a 2,4-dihalogonopyrimldyl-5-methylone radical; these remnants derive z. B. of the following Pyrimidine pre-bond from: 2,4,6-trichloro and 2,4, f-Tribromopyriiuidine and their Dcrivutcn, which Insertion of approximately liquid quantities leads one the reaction so that (J only one Hnlogonatom with an exchangeable hydrogen atom. the Reaction is in weakly alkaline, neutral to weakly acidic medium, but preferably within the pH Boroichus of 9 to .1. The reaction solution is used to neutralize the one equivalent of hydrogen halide formed either at the beginning a binding agent, such as

in the 5-position, for example, carry the following substituents:) _0, for example, sodium acotal added, or methyl, carboxy, carboxymethyl, chlorine or bromine are added in small portions during the reaction of 2,4,6-chloro-5-bromopyrimidine -2,4,5,6-Te-

trachior- or 2,4,5,6-telrabromopyrimidine, 2,4-dichloro-S-chloromethylpyrimidine, 2,4-dibromo-5-bromomethylpynmidine, 2,4-dichloro. 5-chloro-methyl-6-methylpyrimidine and 2,4-dibromo-5-bromomethyl-6-methylpyrimidine.

The introduction of the aliphatic, reactive acyl radicals The easiest way of doing this is usually by using the relevant acid halides Part of the column anhydrides. It is preferred to work at low temperatures, e.g. B. be »0 to 20 C, and in the presence of acid-binding agents such as sodium carbonate, sodium hydroxide, calcium hydroxide or Sodium or potassium carbonate or bicarbonate in solid, powdered or concentrated form knowledgeable solution added. However, aqueous solutions of are also suitable as neutralizing agents Sodium or potassium hydroxide. The addition of small amounts of a wetting or emulsifying agent to the reaction mixture can accelerate the dissolving reaction.

The amine of the formula (II) is expediently dinzoticrt by the direct method at temperatures from 0 to 15 C, preferably at 5 to 10 C, and couples at temperatures from 0 to about 30 ° C., preferably at 5 to 20 ° C., at pH values of

. | o

Nalriumacetat for weakly acidic, neutral or 25 about 5.5 to 9, preferably at 6 to 7, if the

Coupling component carries a reactive radical X, or 7 to 8, if the coupling component the 2-amino-5-hydroxynaphthalene-7-sulfonic acid itself or an acyl derivative thereof such as acetyl, propionyl, Ethoxycarbonyl or methoxycarbonyl derivative used The / ur neutralization required alkali can before the coupling z. B. in the form of sodium bicarbonate or added in small amounts during coupling.

If Iran uses a 2-acylamino-5-hydroxynaphthalene-7-sulfonic acid as the coupling component, the acyl group must be split off after coupling. B. in 2- to 1 () ", hydrochloric or sulfuric acid, at temperatures of 70 to 100 ° C., or in a chemical medium, e.g. II in J:> i 10"., Ii> er, preferably M J- to>'\, igci, N at ι ium II, dl o \ id or potassium hydroxide solution, at temperatures of 80 C to / ur the boiling point of the solution, preferably at 90 to ¹ ) 5 C, are carried out. The cleavage of the acyl flu in the sulfatic dye is carried out in an alkaline medium, e.g. B. in 1 to 5% sodium or potassium hydroxide solution. at ¹ M) up to 100 C.

As sulfate z. B. in question: concentrated sulfuric acid with a content of 43 to HH) IO. Oleum preferably from 0 to 25 ",,, or (.'hlorsulfiuisäure. / Weekly one leads the Sulphation at 10 to 80 C. preferably from JO to 50 C. when using concentrated sulfuric acid, b'w. at (»to tu (. if 111.111 oleum or chlorosulfonic acid vei wendel After coupling or after sulphation udei n.-ieli of the Finfiilinimi four llnippeX can use the MiMio.i / ofarbslollc, im ihien uas.et is'en solutions' u ei kiii.il'm: by adding um SaI / deposited, referring to .iblillrierl, if applicable L ", \\ a. ·, IkMi and then üeliinknet graze

They suit .L Ii to I in In 11 um! eder. / 11 ui I äi ben, Kl'.il / vu nder lUdiuiken um WnIIe ₁ Sei.Ie. -uiilu-Ii -.- hen IVI \ aniidf.i, 1 i η and li-.ein from n-iliii heliei oili 1 ■ iei! i nei ierlei ('e.iiilir,. · Il llaimiw nlL, 1 a.

I lalll. \ l .-. kl'si-llΛ Uli Kliplci Ii. \ i'll '' ■

v \ ie Min (ieniisi hay and new <

weakly alkaline reaction, for example in the pH range 4 to 9. The carboxylic acid chlorides are used for acylation as such or in double to five times the amount of benzene, chlorobenzene, methylbenzene, Dimethylben / ol or acetone dissolved, in the wobbly, well-buffered solution of the body carrying the amino group dripped in, ζ B. at a temperature of

2 to 5 C. Acylation can also be carried out in the same way perform with the anhydrides.

For the introduction of the heterocyclic, vacakive acrylic radicals, such as. B. the 2,4-dichloro or 2.4-dibroinpyrimidyl-5-carbonyl- or the 2.3-dichloro- or 2.1-dibromo-allylic carbon> l- or (> In addition, the acid halides are expediently used. preferably the acid chlorides. The acid halides can be used as such or in the form of a group. in an organic I ostbigMiii; te! wv dioxane. Ac '.' On Benzene. Ί "« »Ίΐ!» Ί ■ '.. I use iilorhenzol uiui do implementation 1111 temperature range from 0 to about 60 C. preferably at 0 to J> C for the 2.4-dichloro or J.4-1) ibroiiip> riinidin-5-caibons.iiiieh. 1 iogenide. b / w. at JO to S-S ('for the 2nd MiiLiilor- or 2,3-I) ibromchino \ alm-6 caiboiis.iure or (l-sulfonsiiurehii, lüeiude and with a pll value / wipe

3 and S. preferably run between 4 tuul λ. Implementation with the. '. t dichloro or!. t-tue

bromcliiiii> \ aliu di.nv. van.ilen k.iuii in the same way aiisgefüliii wenkn

The 1 iiiliihi im .:, 111 .. i »ihalu ·. 11 v.iiiui 1.;. '. id best in 'valiin'em medium Ki etv. 1 (1 l and with sehwath s.uiivi l'c.ikiion. ■ M be
between 3 and (>, \ im i'vn.iiniiien
das ('\ .111111 halide al. .olclie. 111
in an Oiganic I o-.ung .milk

VlL ¹ Iv) H. l-'for the piiiiiäreii koutl 1
one (',, min lialoüi uiil ·. \ wihll 111.in

reiuper.ilnr ν >> ιι Ί1) to (U ι 'and

50

venveiidet ι μ 111 inler i. in

'.mi I In. '.'. waliieiiil liii .Ii
|> \ riniiiliiK- I eni |) ei.iliuen.
am iiccitMu lestin -. i 11 l I Im i
ilainpllliii.hliiiki il a. ·, lnei
■ ". ··. at the:; . ■■ · !:! ii-.: v .'- ek-n '.- rl
Ι-.ιιΙιΚί .Hi -. W πι -Iri.ii ii. IU

, \ laii
'.iei

; '■.!. Ι I. /. I.
■ ιΐίΐΊι .pi mink U-am lu-.lv'ii a ·. inen pll Wen iiiul 1 etiahalvii'en-κη M) nntl I (in (l.nhluk aiii the Wa ... er I I.1I0 ;. eii [-. i ι mi I mc i-.i ll. mil. · Ϊη. · Ι.ι ίϋκΊ.ΠιιΙΊ l ₁ Ii ίι .π! Κικ-π 1 lurch

ti

νΐ.

bilileu

heseii

w and in particular to the filrbon of natural or regonerior cellulose according to the exhaustion method.

The bulk goods are during or after the Fiirben or Kloizon, or the pressure is oinor Subjected to heat treatment in Qcgonwarl by acid-binding agents. When coloring, padding and You can print on the network, leveling, thickening or other commonly used ones Use textile or leather milks. For the natural and synthetic polyamide fibers, acid-binding agents are expediently used which give a pH of 5 to 8, e.g. B. acetal or phosphate buffer, hexamethylenetetramine or, especially if acetic acid has been used for coloring, also sodium bicarbonate or carbonate, while for the cellulose fibers sodium bicarbonate, carbonal, octasilicate or hydroxide, trisodium phosphate or the corresponding potassium compounds come into question.

The dyeings and prints on cellulose fibers that are obtained have very good wet fastness properties (Wasserechlhcil. Fastness to washing at 95 ° C, fastness to perspiration, fastness to soda and boiling) as well as good Friction. Sulfur, chlorine bath water and dry cleaning components.

The new dyes reserve acetate and triacclate artificial silk. Polyacrylonitrile fibers and linear aromatic polyester fibers. In comparison with the next comparable reactive monoazo dyes, which have an alkoxy radical such as Cli} O - or C ₂ H _{5 - O - in place of the radical HO 3} SO — AO—, but instead a sulfonic acid group attached to the benzene, are distinguished the dyes obtained according to the invention are characterized by better solubility in water and a higher degree of fixation on cellulose fibers. Compared to the dyes obtainable from French patent specification 1,221,621 and the French supplementary patent specification 75,771, the new dyes also have better solubility and, surprisingly, a higher degree of fixation

In the following examples, the parts are parts by weight, the percentages are percentages by weight, and temperatures are given in degrees Celsius.

example 1

47.x, parts of 2-amino-5-h \ diox> naphthalene-7-sulfonic acid are dissolved in 800 parts of water by adding 10% sodium sulphide solution in a weakly acidic reaction. 43.6 parts of 2.4.5.6-telrachloropvrimidine are then added and the mixture is stirred at 50 to 60 for a few hours. The pH of the reaction mixture was kept between 4.0 and 4.5 during this period by the dropwise addition of dilute sodium carbonate solution. After the reaction has ended, the 2-trichloropyrimidylamino-5-hydroxyn; phthalic-7-sulfonic acid sodium is completely precipitated by adding sodium chloride, it is suctioned off, washed with a dilute sodium chloride solution and dried. In the meantime, 23.3 parts of the acid sulfuric acid ester of I - / \ mino-4- (2 "-hydroxyeth-ON \! -Benzene are dissolved at room temperature in 400 parts of water with the addition of 4 parts of sodium hydroxide. 6.9 parts Nalritminilril added. The solution is now in a template, ordering of parts 2S / säuie 30 "and 50 iiigcr Sal Ί rush lis. zugetropfl. The resulting suspension is up to the complete Diazoticrung at 5 to 10 'wcilergertlhrl.

42.3 parts of sodium-2-trichloropynmidylamino-5-hydroxyn-phthnlin-7.sulfonal are stirred into fi () 0 parts of water at room temperature. The suspension is crwiirmt αιιΓ60 to 70 'until everything is dissolved, the solution is cooled to 20 and crosslinked within 30 minutes with the diazo suspension, which is allowed to run in in a thin stream. At the same time, 20% sodium carbonate solution is also added so that the pH is constantly 6.5. After coupling has taken place, the reagent mass is warmed up to 70 "and the mono-oaf formed is precipitated by adding sodium chloride. It is then filtered off and dried. Fr is a red powder that dissolves in water with a scarlet color and consists of cotton and fibers regenerated cellulose dyes in scarlet shades.

The dye obtained dissolves in water 30 to more than 50gI and has a high degree of fixation on cellulose fibers.

Staining instructions

2 parts of the dye described above are dissolved in 4000 parts of softened water at 40 ° 100 parts of pre-wetted mercurial cotton cloth are brought into the bath. HO parts of calcined material are added Sodium sulfate and 30 parts of calcined sodium carbonate and heated the bath in 30 minutes aiii 100, after 10 or 20 minutes 110 or 100 parts of calcined sodium sulfate are added After the high temperature has been reached, 50 parts of calcined sodium carbonate are added and wrap the bath for 1 hour at the boiling temperature. The dye is then removed from the liquor, flushed with water and dried. the Preserved scarlet Fäibunt .st light and wet real.

!. The fixation ^ (1 d · ν new dye clearly exceeds those of cnispnvhemv'i ^';.. Ϊ́ι1> · material "with a Ätlio \) group in the para StclluPi! .ir ΛΌΐτί; \ j; c and a sulfoiis.iine group in the ortho position to the a / o group.

Example 2

The according to the information in Example 1 achievable Diazo suspension is at 5 to 10 with a neutral Solution of 23.9 parts of 2-amino-5-hydroxynaphtha lin-7-sulfonic acid in 500 parts of water and 13.5 parts 30% sodium hydroxide solution combined. DureT Gradual addition of sodium bicarbonate keeps the pH between 7 and 8. The amino formed Nionoazo dye is made with the help of sodium chlorine deposited and abliltrierl.

The fillet residue is in 1000 parts Wassei dissolved neutrally and within 2 hours in an ice-cold suspension of 20 parts of cyanuric chloride ii Go 100 parts of water. By adding 20% igei Sodium carbonate solution is kept at a pH of 4 to 5. The suspension is stirred at 0 L '. until wedge AminoazofarbslolTnielir is present. warmed dam to 40 and mixed with the solution of the sodium salts from I 7.3 parts of l-A.min; i-benz.ol-3-sulfonic acid You rested for 4 hours, doing the pulling The pH value is 20% lower at about 7 hull. After the end of the middle of the day aibsloll fromj.vsal / en abliltiicil and ge

tioeknel. You get a dark l'uhei. that ii

e ι r ii η η
ι-

Water with a scarlet color dissolves and cotton and fibers from regenerated cellulose in scarlet Tones colors.

B e i s ρ i e I 3

The aminoinonoazo dye obtained as described in Example 2 is dissolved in 1000 parts of water dissolved neutrally and within 2 hours in a solution of 34.3 parts of 4- (4'.6'-dichloro-l ', 3 \ 5'-lriazinyI-2'-amino) -benzo! -l-sulfonic acids! Sodium in 350 parts of water at 35-40 is added. The whole thing is stirred for a few hours at 35 to 40, keeping the pH at 6 to 7 by adding 20% sodium carbonate solution. To When the reaction has ended, the dyestuff is salted out, filtered off and dried. You get a dark one Powder that dissolves in water with a scarlet color and regenerated cotton and fibers Cellulose stains in scarlet tones.

Example 4

15.3 parts 1-amino-4- (2'-hydroxyethoxy) benzene are dissolved in 300 parts of water and 20 parts of 30% hydrochloric acid at room temperature and diazotized by Zugabc of 6.9 parts of sodium nitrite at 5 to 10. ¹ The diazo solution thus obtained is allowed to run slowly at 5 to 10 into the neutral solution of 30.3 parts of sodium ^ -acctylamino-S-hydroxynaphlhalin ^ -sulfonate in 500 parts of water. The pH value is kept at 7 to 7.5 by adding sodium carbonate solution at the same time. The dye formed is salted out and filtered off with suction.

The dye paste is in 600 parts of a 2% sodium hydroxide solution for 2 hours at 95
touched. After this line, the acetylation is complete. The hot solution is clarified by filtration and adjusted to a pH of 7 to 8. The aminoazo dye is eliminated. Sucked off and washed with sodium chloride solution.

The filter residue is dissolved in 1000 parts of water at 70 and within 2 hours at 70 to 80 mils of 21.8 parts of 2,4,5,6-trachloropyrimidine offset. The pH value is kept at 6 to 7 by adding 20% sodium carbonate solution No more aminomonoazo dye is detectable, the trichloropyrimidylamino dye is salted with Sodium sulfate. The sucked off and dried dye is in a template consisting of 32 parts | 00% sulfuric acid and 32 parts of 25% oleum entered within one hour at 5 to K). The temperature is then allowed to rise to 20 and the mixture is stirred at 20 for 2 hours. The received Solution is poured onto F sharp at 0-5. The precipitated one The dye is then filtered off and dissolved in dilute sodium caibonate solution Precipitation with sodium chloride is converted into the sodium salt. It is then dried and dried. F.r is a red powder that dissolves in water with scarlet fat and cotton and fibers made of regenerated cellulose in scarlet tones Πι rhi

Example>

The slide suspension obtained according to the details of Example 1 is slowly run into the neutral solution of 30.3 parts of nail ium --- acelvlainino-5-hydio \ nuphthalin-7 sullonal in 5 (M) parts of water ^{at s to K)} left By adding sodium carbonate solution at the same time, the pH is kept at 7 to 7.5. The dye formed is salted out and filtered off with suction.

The dye paste is in 600 parts of a 2% sodium hydroxide solution for 2 hours at 95 touched. After this time, the deacetylation is complete. The hot solution is clarified by filtration and the Aminoazo dye is salted out, filtered off with suction and washed with sodium chloride solution.

ίο The filter return is in 1000 parts of water of 40 dissolved, then the solution cooled to 0-5 and within 2 hours at 0 to 5 "with a solution of 16 parts / i-chloropropionic acid chloride added in 25 parts of benzene. The pH value is maintained by adding 20% sodium carbonate solution at 6 to 7. When no more amino monoazo dye can be detected. the solution is warmed up 20 'and salts the / I-chloropropionylamino dye with sodium chloride. The sucked off and dried dye is a red powder, which is in Water with a scarlet color dissolves and cotton and fibers from regenerated cellulose in scarlet Tones colors.

B e i s ρ i c 1 6

The procedure is as in Example 5, but the / i-chloropropionic acid chloride solution is replaced by a solution of 23.5 parts of 2,4-dichloropyrimidine-5-carboxylic acid chloride in 100 parts of acetone. The dye dried at 40 turns red Powder that dissolves in water with a scarlet color and cellulose fibers as early as 20 to 40 colors in scarlet tones.

Example 7

The aminoazo dye obtained as a water-containing filing residue according to the information in Example 5 is dissolved in 1000 parts of water at 40. gives 27 parts of finely powdered 2,3-dichloroquinoxaline-6-carboxylic acid chloride in small portions added and stirred at 40 to 45, until no free amino group is more detectable. During this time, the pH is maintained at 5 to 6 by dropping Addition of 20% sodium carbonate solution. The dye is that described in Example 5 Way isolated. Ur dissolves in water with a scarlet color and staining cellulose fibers in scarlet, light- and wet-fast tones.

Example 8

In example 7, the 2,3-dichloroquinoline is replaced δ-carboxylic acid chloride by the appropriate amount of 2,3 - dichloroquinoxaline - 6 - sulfonic acid chloride or • 6-isocyanate. In the first case one works preferentially at 50 to 55 and in the / wide case preferably at 40 to 45. but the addition of an acid-binding agent is not necessary. Receiving the Dyes are very similar to the dye of Example 7

B c i s ρ i e I 9

The diazo suspension obtained according to the information in Example 4 wild at 5 to U) 'with a nei central solution of 23.9 parts of 2-amino-5-h> ilroxj i> 5 naphlhalin-7-sulfonic acid in .MX) parts of water un 13.5 parts of 30% sodium hydroxide solution are combined By gradually adding sodium bicarboiii If the pM-Wctl is between 7 and 8. The gcbilde

644

367

ίο

Aminomonoazo dye is deposited with the aid of sodium sulfate, filtered off with suction and dried. He 100% sulfuric acid is added to 100 parts within half an hour at 15 to 20 ". Man stir for a further 2 hours at 30 ° and pour the resulting solution at 0 to 5 ° on ice. The precipitated one The dye is filtered off and washed with water. >

The filter residue is mixed in 500 parts of water. The pH of the suspension is determined by Addition of 30% sodium hydroxide solution set to 6 to 7. The suspension is now heated to 70 to 80 ° until everything has dissolved, and 18.4 parts of 2,4,6-trichloropyrimidine are added to the solution. Through Addition of 20% sodium carbonate solution keeps the pH at 6 to 7. If no amino monoazo dye is more detectable, the dichloropyrimidylamino dye is salted with sodium chloride out. The filtered and dried dye is a red powder that turns scarlet red in water Dye dissolves and dyes cotton and regenerated cellulose fibers in scarlet shades.

Example 10

The acetylamino dye obtained as described in Example 4 is isolated and dried. It is in a template consisting of 50 parts of 100% sulfuric acid and 11.7 parts of chlorosulfonic acid at 0 to 5 "entered within half an hour. The temperature then slowly rises Let room temperature rise and the resulting solution is poured onto ice. The precipitated dye is filtered off and washed with water. .The dye paste is in 800 parts of a 3% Sodium hydroxide solution stirred at 95 for 2 hours. After this time, the deacetylation is complete. The hot solution is clarified by filtration and brought to a pH of 7 to 8 by adding hydrochloric acid placed. The aminoazo dye is salted out, filtered off with suction and treated with sodium chloride solution washed. The filter residue is dissolved in KH) O parts of water at room temperature. Within a Hour, the solution is left with stirring in an ice-cold aqueous suspension of 18.4 parts of cyanuric

IO

game RcM Λ SuhstiiuciU Z Kcuklivknmpunentc Way of working
according to Hebeispiel II) III) Uli) (IV) 12th CH ₂ CH ₂ H 2.4. (I-Trichloropyriinidine 1 13th the same H 2A6-trihromopyrimidine I. 14th the same H 2,4,5,6-tetrabromopyrimidine 1 15th the same H 2A6-Trichli> r-5-methyl- 1 pyrimidine 16 the same Il 2 Afi-Tnchlor- i-bromo- I. pyrimidine 17th . the same H 2Α6-Ί richlor-5-ehIormelhyl- I. pyrimidm IK the same H 2Afi-Triehlor-5-earhti \ y- 1 pyrimidine l ^l > the same Il 2A ('- I'rithlor-5-carbo \ y- 1 inelhylpyrimidine 20th CII ₁ CII; CH, Il 2A5, f) -lclradiloi pyrimidine 4th 21 cn, cn
I. Il the same 4th (II.

chloric! come in. A dilute sodium hydroxide solution is added dropwise at the same time the pH value at 5 to 6. After the reaction has ended, the resulting dichlorotriazinyl dye is salted out, filtered off and dried at 30 to 40 in vacuo. It dyes cotton and fibers regenerated cellulose according to the dyeing instructions described below in scarlet shades.

Staining instructions

2 parts of dye are dissolved in 3000 parts of softened water at 40 ^{° C} '. 100 parts of pre-wetted cotton or cellulose tissue are placed in the bath, 100 parts of calcined sodium sulfate are added over a period of 30 minutes and the mixture is heated to 60 "at the same time. Then 6 parts of sodium hydrogen carbonate are added and kept at 60 ° for another half hour 6 parts of calcined sodium carbonate are added in portions over 10 minutes and held at the same temperature for 15 minutes. The dyed fabric is then removed from the liquor, rinsed with hot water and soaped with a 0.3% boiling solution of a non-ionic Detergent, rinse it again and dry it.

A scarlet red lightfast and wetfast is obtained

Coloring. ". . , ,,

^b Example 11

The dichlorotriazinyl dye solution obtained as described in Example 10 is during Stirred for 2 hours at 40 'with 20 parts of a 25% strength aqueous ammonia solution. After finished In the reaction, the resulting monochlorotriazinyl dye is salted out, filtered off and dried. He dyes cotton and fibers from regenerated cellulose according to the dyeing method given in Example 1 in scarlet tones.

The following table contains further dyes which, according to the information in Examples 1 to 11 are obtained and by the alkylene radical Λ, the

Substituents Z, the reactive component on which the radical X is based, the procedure according to a of Examples 1 to 11 and the shade of the dyeing are marked on cellulose or polyamide fibers in columns (I) to (V).

! ■ 'arbtun IVi

Scarlet Scarlet Scarlet « Scarlet Fever ™

Scarlet Rc Seharlaclm Scharlaclm scarlet fever

Scarlet Scarlet

11th

example

Remainder A
(D

22nd
23
24
25th
26th
27 - CH ₂ - CH ₂ -
the same
the same
the same
the same
the same 28 -CH, CH ₂ -CH, 29
30th
31 -CH ₂ CH,
the same
the same 32 the same 33 -CH ₂ -CH, - 34
35
36 the same
the same
the same 37
38
39 the same
the same
the same 40 the same 41 the same

Continued 12

Substituent Z (H) Reactive component (Hl)

Cl

Br

-CH ₃

-C ₂ H ₅

- COOH

H H H

H II

H H H

H H H

H H 2,4,5,6-tetrachloropyrimidine

the same

the same

the same

the same

2,4-dichloro-5-chloromethyl · 6-methylpyrimidine

2,4,6-trichloro-5-brpm-

pyrimidine

Chloroacetic acid chloride ii-chloroacrylic acid chloride Cyanuric chloride, then

fi-hydroxyethylamine cyanuric chloride, then

Methylamine 2,4-dich 1 or-6- (2'-carboxy-

phenylamino) -l, 3,5-triazine bromoacetic acid bromide acrylic acid chloride 2,4-dichloro-6- (2'-suifoälhyl-

aminoM, 3,5-triazine cyanuric bromide / i'-bromopropionic acid chloride 2,4-Diehlor-6-methyl-

pyrimidine chloride -5-carboxylic acid-2,4-dichloro-6-carboxymethyl- amino-1,3,5-triazine

Cyanuric chloride, then

Di - (// - hydroxypropyl) amine

Working method according to the example

(IV)

Color (V)

4th
4th
4th
4th
4th
¹ scarlet
scarlet
scarlet
scarlet
scarlet
scarlet 1 scarlet IO Ui Ui scarlet
scarlet
scarlet 2 scarlet 3 scarlet 5
5
3 scarlet
scarlet
scarlet • OK
5
6th scarlet
scarlet
Scarlet rol 3 Scarlet Il Scarlet

Claims (1)

Claims: 1. Process / for the preparation of reactive dyes !! the formula HO ₁ SO Λ Ο NHX wherein Λ is an optionally one carrying alkyl radical with 2 to. uiomen. Z hydrogen. Chlorine, bromine, low-molecular-weight alkyl or - COOII and X have at least one sub- (to luenien and / or an addition enabled Mchrfachbindungenlhallcnden reads means that by g e k e η iw e i c h η e l. that one I mol 2-Amino-5-hydio \ ynnnphlhalin-7-sulfousiiur in any order with at least 1 mol of one h * Acylating agent umsel / l, which after the um set / ιιημ or at least one as an anion ahspallharen Sulislitiicnlcn and / or an additiousnihige Contains multiple bond and with I mol d Diuzovci bond from an amine of the formula O \ Nile. (U) where Y is WavseislolT or S (), II. orlho position / ur ll> dro \ ylgruppe kuppelt tu if Y is for a water hazard. with a SuI tii'rungxiiiiiicl Kh.nnlell Z. Alteration of the ability according to claim 1. characterized in that mim I moles of Diazo compound from an amine of the formula (II) with 1 mole of 2-Ac \ 1 amino-5-hydroxynaphthalene-7-sulfonic acid couples, cleaves the Aeylgruppc and the amino group with at least 1 mol of an acylation mill, which after the implementation of at least one substituent which can be split off as an anion and / or an add contains multiple bonds, and. when Y is hydrogen, the dye into a any stage of the replacement of the acyl group by the substituent X with a sulf ticrungsmittcl treated.