DE2100080C3 - Water-soluble reactive monoazo dyes and their copper complex compounds and processes for their preparation - Google Patents

Description

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5 6

The invention relates to new, water-soluble reactive mono-olearic studs of the formula I.

OH X

HO ₃ S! Il ^NN - Y St.

R- N SO, CH, CII ₂ '-O- SO ₃ H

CO CW ₂ - (CH ₂ I ₁₁ -SO ₃ H

in which R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X is a hydrogen atom or a hydroxyl. Mcthoxy-. Ethoxy. Carboxyol or sulfonic acid group. Y is a hydrogen atom or a Methyl, ethyl, methoxy. Ethoxy or sulfonic acid group and /; Means 0 or 1, and their copper complex

dyes of the formula 2 ,,

Cu

O j O

IK) ₃ S - '/ - i ■' ^NN -V 12)

RN SO ₂ - CW ₂ CII ₂ O SO ₃ II

CO-CH ₂ ICH ₂ I ₁ , SO ₃ II

in which RX Y and η the above of the formula (■>

Have meanings, as well as procedures for their Her- OH

position by 30

a) an amine of the formula 3 - \

HO ₁ S - ^: ii | (61

X '■'. "W

: R N

"- ^{N -} YC) CO CW ₂ (CH ₂₎ ,, SO ₃ H

SO ₂ CII ₁ CH ₁ O SO ₁ H in .velcher R and / 1 the meaning mentioned above

tungen, kupnelt and the / f-Oxyäthylsulfon-

in which X and Y converts the aforementioned Beden group into the ..'- Suintoathylsulfongruppe Hingen, dia / olierl and with an A / okompo- and optionally if X is a hydrogen atom component of formula 4 or a hydroxyl. Methoxy or Atiioxygi group

means in general X = H in the presence of water

^ "hydrogen peroxide with copper-releasing agents

_/; ,). _K 45 implements or

, '''λ ⁷ c) an amine of formula 7

HO ₃ S -! -_) [ _λ I; (4! _Χ

R -N

CO CII, (CH ₂ ) ,, - SC ₃ H " -, ■; - \ (7)

couples and, if necessary, if X is a water ²

Substance atom or a hydroxyl. Mcthoxy- or Ath- in which Y the meanings given above

Oxy group in the case of X = H in the presence of ss hai and X means a water atom or a llxdrow-,

of hydrogen peroxyl with copper-releasing Mciho \\ - or ^: \ thoxygnippe means, dia / olierl.

Agents or with an azo component of the formula S
n) an amine of formula 5

Oll

X ho

IFN .. ^{ii ()} ^ ^S '

■ '\ ni

R \
SO. CII, CII. Oll 1 ...

i'o Ui, itll.l ,, M) Ji

• 1: which X uiul V the mm-dividing called heal
iiiii '.' en have diazoiierl. mil an Azi'kiMnpiMieii !, ' ^{: i} i' ekini! - 'ni -I n die,'eiiei> iien '.'eiMiuiie', Re

21 OO

strength have dome !, ilen dye obtained by acylation of the corresponding monoamino-L ^- r I ormcl '' I-naphlhol-monosulfonic acids in water with acylations

liei imi'smilleln. how OH \

K) ₁ p
RX

N N

SO, CII, CII, Oll

2s

CO CII. ICIK) ₁₁ SO ₁ II

ml treated with an anti-aging agent and the obtained copper complex dye, given al converted into (essentially organic solvents) into the corresponding sulfuric acid ester.

Monoazo dyes and their copper complex compounds are well known. as azo components N-acylamino- I -iiaphtholmonosull'oi ^ iiucn. such as, for example, 6-acylamino-1-naphthol-3-sulonsätiie. 7 - Acylamino - 1 - naphthol - 7> - sulfonic acid. ^ -Acylamino-1-naphlhol-3-sulfonic acid or X-Acylimmo-1-naphlhol-5-sulfonic acid. contain, which as \ c \ best preferably have the acetyl, propionyl and Ben / oy I radicals.

However, dyes of this type are in the alkaline range. like him for Klolzflolten or Eärhcbiider generally in I-'raue, only a limited one I osliclikeii.

The / in the production of the new ! ■ arhsiolTc a / usei / ends monoamino-1-rraplitholinonosullonsiiuren can easily be acylated in water. As the technically most important monoamino-1-naphihol monosulfonic acids come the 5-amino-1-naphthol- .1 -sulfonic acid. X-amino-I-naphthol-S silicone acid. (1-Amino-1-naphthol-? - sulfonic acid πη, I ■ "-amino-l-naphthol-.i-sulfonic acid in question.

A / o components derived therefrom. the new monoazo dyes !! or their KupferkiMüpi-, \ en / iii round, correspond to the general i ornicl

(I CII, CO Cl

ei cn, cn, co ei

in (iegenwarl of siiurebindenden Mitleln. as NaIlCO _1. KIICO, .na CO ₃ or CaCO _{1 1.} 1 in the pi-Bc rich 5 to S to the general Chloracylaminoderivaten l-'ormel

Oll

i ^! N co cn, | cii, j "ei

in which / 1 means O or I, and others Reaction after possible isolation, in aqueous solution with sodium sulphide at elevated temperature. After removing an existing excess of sodium sulphide used, these azo components can isolated or used directly for the coupling reaction.

To produce the new monoazo dyes, these azo components are known per se! Way with diazonium compounds of the general formula

NH,

SO, ClU CII, O SO, H

\ CO CII, ICH,] ,, SO ₁ H

in which η is O or 1 and R is an Aikyiresi of 1 to 4 carbon atoms. They are produced in a manner known per se, for example in which X and Y have the meanings given above / u monoazo dyes! united. In the cases where X is the hydroxyl. Methoxy or ethoxy group means, can be obtained therefrom by cropping, ie by the action of copper salt or other copper-releasing agents in Raumbz.w. recovering temperature and possible splitting off of CH ^ OH or ethanol, the copper complex dyes of the general formula

HO ₃ S- [CH ₂ L-CH ₂ -CO-N- ^

Cu

7 ^x ,

O /

■, rN-Nt " SO ₃ HY SO ₄ -CH ₂ -CH ₂ -OSO ₃ H

in which R. Y and η have the meanings given above, are produced. A> \ eitci2r way. To get to such copper complex dyes, there is oxidizing copper

609 630/1

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ίο

tion \ iiii such N-Ac_ \ lamino-1 -naphlhol-inonoazofai hstoffen. where X is em water salon. the ah » the general formula

IK) ₁ SI Cl I, | "CII, CO N i! J. NN

SO ₁ II Y

'! SO, CH, CM, OSO ₁ II

correspond, in which R, Y and ii have the meanings given above. In contrast to dyes which are derived from N-acylamino-1-naphthalenedisullonic acid and which only give red to blue tones, the new process can produce dyes with shades of yellow orange to loosely blue.

In contrast to dyes with N-Acvlamino ribs without additional sulfonic acid group in the acylresi the new dyes are still gul in water even after splitting off the sulfuric acid selenium soluble.

The new, readily water-soluble dyes can be salted out, for example with sodium chloride. Potassium chloride or mixtures thereof or isolated by spray drying. They make new ones Reactive dyes are, according to the usual Ver drive on wool, silk. Polyamide fibers and especially cotton or regenerated cellulose

Is fibers with I III alkaline agents in the room temperature oiler elevated temperature chemical lixie i let. Come as an alkaline agent for this purpose, for example, sodium bicarbonate, sodium carbonal. Sodium hydroxide. Potassium hicarhonate. Ka

ίο lium carbonal. Potassium hydroxide. Trisodium phosphate, sodium silicate and sodium trichloroacetate.

In the following some typical Examples of the reactions on which the discovery is based ! ions described.

(above the well-known dye of the formula

OCIl,

OH

■ N N:

S (K ^{S <)} <^{N; 1}

CII,

CII. OSO, N, ι

Nile CO (II, CH, COONa

the dyes according to the invention are more similar Structure due to a significantly lower level of liability against calcium and magnesium ions. whereby the new dyes are also not softened Dye baths can be used. In view of the fact that the well-known dye besides of the side chain mentioned, there are also two highly water-soluble ones Contains groupings (a sulfonic acid and sulfato group), the said must be superior Property of the new dyes are considered surprising.

example 1

0.1 mole of 1-amino-3 - // - sulfatoäthylsulfonylbenzol are neutralized and at 20 "C in 50 cm ³ of water with 60cm '10% sodium carbonate solution to a pH value of 6.5 dissolved after addition of 20 cnr ¹ 5N. NaNO ₂ is stirred into a mixture of 125 cm ^{3 of} 2N HCl and 100 g of ice. After 30 minutes, the excess sodium nitrite is destroyed with a little sulfamic acid. 0.1 mol of 2-sulfoacetylamino-5-naphthol- 7-sulfonic acid and slowly adjusts to a pH of 3.0 to 4.0 at 0 to 10 "C by adding a saturated solution of sodium acetate dropwise. After the coupling has ended, the dye formed is precipitated with sodium chloride and nitrated and washed with saturated sodium chloride solution. After drying at 50 to 60 C it is an orange-brown powder. That on cotton from alkaline liquor

so gives orange-yellow colorations. These colorations have good to very good light fastness and light fastness, where wet fastnesses are understood to mean both manufacturing and usage fastnesses. In terms of production fastness, the fastnesses to treatment with acids or alkalis, Sulfur dioxide or sulphurous acid and their salts and the fastness to heat treatment, in terms of fastness to use, the various wash fastness, perspiration fastness, wet light fastness, Fastness to perspiration light, fastness to rubbing, fastness to organic solvents and fastness mentioned in relation to chlorine-containing aqueous media and in relation to seawater.

The dyes listed in the table below can be prepared in a similar manner, where instead of l-amino-3-ff-suIfatoäthylsulfonylbenzol the equimolar amounts of the listed amines are used.

11th

Oll

IK) ₁ S Nile

COCH ₁ SO ₁ II

s-j I

1) | .l

II, N

ClI ₁ O

IA

12th

Nile,

SO, CII, Cn, OSO ₁ II

SO.CH.CH.OSOJI SO.CII, CH, OSO (H.

CII ₁ O SO, CH, CH, OSO ₁ II

I .iihlun

yellowish oniime

yellowish onmtie

dissolute () i; mue

reddish

ilesul.

CH ₁ O Sn ₁ CHjCH ₁ OSO ₁ !!

II, N CH ₁

clear

yellowish

Red

desD

the same

the same

the same

CH ₁ O SO ₂ CII ₂ CH ₂ OSO ₁ H

II. N OCH,

C!

SO ₁ CH ₂ CH ₂ OSO ₅ H

CH.,

NH ₂
H ₃ C- / V- SO ₂ CH ₂ CH ₂ OSO ₃ H

SO ₁ H
H ₁ N- /,

SO ₂ CH ₂ CH ₂ OSO ₃ H

clear

yellowish ··

Red

yellowish Oransie

- SO ₂ CH ₂ CH ₂ OSO ₃ H orange

orange

yellowish orange

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I οι tsei / mm

Il i. '.' Ki'llll "ΊΗΊ

1 -.nhliui .! il H.iunm ι

on

S <). (11 <II.I) SI

Nile C (KIUSO, 11 <) (II,

rolslichigc orange

CO! HI

of"!.

() ian <jc

SI KCH. (I I I) S (), l I

I I X

Sl). (Ill I l. () S <

Oranuc

SO ₁ II

SI Kl Il Cl |. (> S <

<> iani.'e

Cll

S (M I I. ('I I. ι ■ ^. Ι ι. I I

IU ι s ρ ι c! Γ

0.1 mol 1 - / \ mmo-4- _i ; -sulfatoälhy] sullon \ Iben / ol graze at 0 to 5 C in 75 cm ^{3 of} Zn-HCl. and 50, l; is with 20 cm ^{3 of} 5n-NaN () _; dia / listed. The τ-schutö in nitrate is reduced with a little amidosulloid acid. Trail into the suspension received! 0.1 mol 2 -,; - sulfopropiomlamino-5-naphthol- "- ^ uifonsaure and corrected slowly at 0 to 5 C the pH value up to 3.0 mil 10% sodium t'ormate solution. The coupling is after a short time time stopped. It is with some sodium carbonate to a pll-WCIT of 4λ to 5.0 and the resulting fall! arbsii! ' mn potassium chloride. After drying in a vacuum at 50 to Wl C you get 4? one a light-brown powder, which on tree people: n Presence \ of sodium carbonate from alginate -. thickened paste gelhorange prints with good bi: sein -juten light and wet fastness results.

! ii similarly the following can be used the dyes listed in the label are manufactured. where instead of 1 -amino-4-; i-suifato; itn> I sulfonylbenzene, the equimolar amounts of the amines listed in the table are used.

Example.-Xzoknmpone-itc

Diazo component

hue

on cotton

OH

H, N

Sa-CH ₂ -CH ₁ -OSO ₃ H

SO, H

NH-CO-CH ₂

CH ₁ -SO ₁ H yellowish orange

ortsci / ung

16

. ■ i-'picl Λ / ok ι Mil pi »η cn Κ! •" iirbliin ; ιιιΓ H.ium «

on NMJ,

SO ₅ II

NU CO CH,

cn,

SO, CH, -CH, OSO., Π gelhstich

O ran nc

23 ilcs.iil.

24 dcsiil.

NII,

CH ₁ O SO, CU, CH, OSO., 11 reddish

orange

OCH ₁

H, N SO, CIl ₁ CH, OSO., H reddish

- Orange

OCII,

11, N-- 'SO, CH, CH, OSO ₁ H "clbstic

Red

CW,
OCH,

. SO, CH, CII, C) SO ₁ H «clbstic

OCH,

II, N

Cl

cn.

SO, -CH ₂ -CH, - OSO ₁ II

orange

dcsül II, N

SO, CHj-CH ₂ OSO ₁ Il orange

NII,

: r, the same

||, C SO, CII, CII, OSO ₁ II orange

SO ₅ H

11, n

I. \

s (i cn cn., oso, 11

S (). CW. CIl. OS O. ι I
() (!!,

1 lit si ic

21 OO 080

continuation

t'ispiL'l \ / okt »mpc> nen! e

Kiihtnn .in! "H.iiin

OH

SO, H

M) des «!.

NH-CO ClU

ClU SO ₁ H

11, N COOII

SO, CH, CU: OSO ₁ H

() l.l! l'JC

COOII

SO, CH _: C \\ _: OSO ₁ H orange

SO ₁ H

II, χ SO, CW ₁ CW ₂ OSO ₁ H orange

SO, CH, CW, OSO ₁ H

the same

Π, Ν CH,

orange

Example 33

0.1 mol of 2-amino-4- _/ ; -sull'atoäthylsulfon \ lphenol ν are diazotized at 10 to 20 ° C in 125 air '2η-HCl with 20% 5U-NaNO and a small excess in the sodium nitrile with a little amidosullonic acid removed. To the diazonium solution add; one 0.1 mol of 2-sulfoacetylamino-5-naphthol-7-sulfonic acid and 20 g of crystalline. Sodium acetate and adjusts to a pH of 7.5 with sodium carbonate solution. The mixture is subsequently stirred at room temperature until the coupling has ended. Now one carries 0.1 mol of crystalline. Copper sulfate and 25 g of crystalline. Sodium aeetai and stir until the coppering is finished. The resulting copper complex dye is gelatinized with potassium chloride. filtered off and washed with saturated potassium chloride solution. After drying in vacuo at 50 to 60 ° C., a red-brown powder is obtained.

which dissolves easily in water and on cotton <xlei Spun rayon in the presence of sodium bicarbonate gives red prints with good to very good fineness. Is used instead of 0.1 mol of 2-sulfoaeeiylamino-5-naphthol-7-sulfoic acid 0.1 mol of 2-sulfoaectyl-methylamine! -5-naphthol-7-sulfonic acid or 0.1 mole of 2-sulfoacelyl-butylamino-5-naphthol-7-sulfonic acid. in this way one obtains dyes with similarly good deficiency properties.

The dyes listed in the following table can be prepared in a similar manner, if instead of 2-amino-4 -, »'- sulfatoethylsulfonylphenol the equimolar amounts of the amines mentioned there or instead of those in Example 33 used 2-suIfoaeelylamino-5-naphthol-7-sulfonic acid the equivalent amount of 2- / i'-sulfopropionylamino-5-naphthol-7-sulfonic acid begins.

Example \ / c component

Oll

I) i; i / overbindcnle \ tel; ill I; iibiiiii, ml
li.uimuolle

OH

CH,
NC (KII,

CiI, SOJI

IN

SO. (II. (II, OSO ₁ II Cu Honlr

Il \

(H ₁ (MI (H (H. OS (), l I

I .ii-.Hi I111.V,

\ i.-lei!

"Ml CII. 1 ¹ MI ₁

\ I-IeII

sfsi

21 OO 080

) l.! / i'kiMliptiDUI

NK-I.ill I aihlim .nil '

Oil

Ml.

HO

Nile CO CU.

Ml. SO ₁ I.

SO. (I! Cll · OSO ₁ II Cu W.! IiMidii; ji> RH

ilc-tit.

(U

H (I Rl 11

OH

ill · «. ·!

OH

t H, OSO, Il

Ml.

oil!

Vk-Il-U

IH ι, S

ΚΊΙ, Ι, CIl, N CO Cl

SO (M. CH, OSO ₁ II

Cu

<Il

S (I

Example 41

0.1 mol of 2 - / \ mino-4 - /; - sulfatoethylsulfonylanisole are at 5 to 10 "C in 70 cnv '2n-HU with 20 cm'5n-N; iN () _; diazoticrl and the excess of nitrile with a little amidosulfonic acid / At 0 ° to 5 ° C., 0.1 mol of 2-sulfoacctylamino-5-naphthol-7-sulfonic acid is added and the pH is adjusted to 4 to 4.5 with sodium acetate 30 g of crystallized sodium acetate are added and the mixture is refluxed for several hours until the copper complexation is complete. The resulting copper complex dye is precipitated with potassium chloride, filtered and washed with saturated potassium chloride solution. After drying in vacuo at 50 to 60 ° C., a dye is obtained which has that obtained according to Example 33 is identical.

hl.iii-.lii Ni. .IcIi

Example 42
Moles of 1-amino-2,5-dimethoxy-4 -; - sulfaio-

Ethylsulphonylbenzene at 5 to 10 C in 70 a ³ 2N-! ICI with 2OcIiT * 5n-NaN () ₂ dia / olierl and the addition of nitrile with a little amidosulphonic acid. At 0 ° to 5 ° C., 0.1 mol of 2 -, - sulfopropionylamino-S-naphthol-7-sulfonic acid is added and the pH is adjusted to 3.5 to 4 with crystallized sodium acetate and the mixture is then stirred until the coupling is complete ! is. 25 g of crystallized copper sulfate and 30 g of crystallized sodium acetate are then added and the mixture is refluxed for several hours until

I ₁ O the copper plating is finished. After cooling to room temperature, 2.7 g of sodium oxalate are added and the mixture is stirred for 4 hours. The precipitated copper oxalal is filtered off and the resulting copper complex dye is isolated by spray-drying.

4s voltage. One that is very readily soluble in water is obtained Dye, made of cotton in the presence of sodium carbonate, in blue-tinged violet tones with good to very good wet and light fastness stains those listed in the table below Dyes can be obtained in a similar way:

Example Vnkoiiiponenle

) ia / (iki'i

Metal i; ii hum on cotton

IH i, S

Oll NII C. (I. 1 11 Il
1 S ()

OCII,
11.N SO (II. CH. OSO ₁ Il (η Hm

K Il

so ι H (H. OSO ₁ II (Ii

ortset / unu

. '! spiel \ / nk ι till pi HlL ^- Il k'

) |.! / <'tv'Mlip.

McKiIl l.irhh.n .ml

OM

IK) ₁ p

Oil

IM) ₁ p

Nile ((I III, SO ₁ II

NI) CO CII.

ClI, SO. 11th

OCH,
|. \ SO. (II; CIl. OSO ₁ II Cu

OCH,

Vuilcll

SO. CII. CU, OSO ₁ II Cu

to do.

11, \ Si). (! I, (H OSO, Il Cu Hm, I ,.

ilcsiil.

Example 49

0.1 mol of 3- / i-sulfatoethylsulfonylaniline are dissolved at room temperature in 50 cm ^{1 of} water with 60 cm ^{1 of} sodium carbonate solution to pH 6.5 ^{, mixed with 20 cm 3 of} 5 H-NaNO- and mixed in a mixture of 125 cm ^{1 2N} -HCl. H) Og ice and 0.5 cm ^{3 of} 5N NaNO ₂ stirred in. After 15 minutes, the excess nitrite is removed with a little sulfamic acid. 0.1 mol of 2-sulfoacetylamino-8-naphthol-6-sulfonic acid is added to the diazo suspension and the pH is slowly adjusted to 3.5 to 4 at 5 to 10 ° C. with crystallized sodium acetate The coupling is complete. The resulting dye is precipitated with potassium chloride ims, filtered and washed with saturated potassium chloride solution. After drying, a brown-orange dye powder is obtained which is very easily soluble in water and which is made from alginate-thickened paste in the presence of sodium bicarbonate on cotton rolish orange Color tones with good to very good subtleties result.

Example 50

0.1 mol of 4 - / (- SulfatoäthyIsulfonylanilin are in

0 to 10 C in 70 cm ³ Zn-HCl with 20 cm ³ 5n-NaNO, dia / otiert. the excess of sodium nitrate is removed with a little amidosululonic acid. 0.1 mol of 2- / i'-sulfopropionylamino-X-naphthol-6-sulphononic acid is then added and slowly adjusted to a pI value of 2.5 to .1 with sodium formate and stirred until the clutch has ended. It is neutralized with a little sodium carbonate to a pH value of ^4.1 and the dye solution is evaporated in vacuo at 50 to (iO ('. An orange-colored l'ulu-i. Is obtained which is very easily soluble in water. Cotton is obtained man in the presence of Nail iimicarboiiat roisi ichige () rangcfärbuu! 'cn with gul to very!' iilen

1 li-lii- imil washing hehiling.

oc 11.

(II,

SO, CII. CII. OSOJI

Cn

51

rolsikhr
ν, οΚ-ιι

example

0.1 mol of 2-amino-4- / i'-sulfaloethylsulfonyl phenol are dissolved at 10 to 20 ° C. in 125 cm ^{3 of} 2N HCl ^{with 20 cm 3 of} 5n NaNO-. dia / oliert and the excess nitrite destroyed with a little sulfamic acid. 0.1 mol of 2-sulfoaeelylamino-8-naphthol-6-sulfonic acid and 20 g of crystallized nairium acelate are added to the dia / onium solution and 10% sodium carbonate is added

₄ c solution to a ph Wcrt of 7.5. The mixture is stirred until the coupling has ended. Then 25 g of crystallized copper sulfate and 25 g of crystallized sodium acetate are added and the mixture is stirred at 30 to 40 ° C. until coppering has ended. The resulting copper

complex dye is salted out with potassium chloride. filtered and washed with a little saturated potassium chloride solution. After drying at 50 to dO C, a brown dye powder, the cotton, is obtained after the exhaust process in the presence of potassium carbonate in real bluish-tinted red ions stains.

Example 52

0.1 mol of 2-Meihoxy-4 -, ')' - sulfatoälhylsulfonylaniline are diazotized at 10 ° C. in 125 cm ^{1 of} 2π-Η (Ί mil 20 cm ^{3 of} 5n-NaNO) and the excess of sodium nitrate is taught in with a little amidosulfonic acid -,; - Sullopropionylamino-S-naphthol- (vSdHonsäiin: and 20 <j crystallized Nalriumaeelal '■>> / u uiul sU'lli with NaIi nmuaibonallösmu' au! Omen pi I-Wni from -1 to> »in and stirs until the K ii] i, -iHin: 'liecndi-l isl. Well ν er ^ el / i man mil ^; () ... kn-NlallisiiTk'm Kiipfersullai i'.n.!'O;: kristalhsn-riein NaIi iuinaccl.il and cooks euiü'e ^ imulen .1111 '' iiik -'- s lluss. To cm 'In-' matojiianim das Fnde dct kup-Γ1ΊΊ111; ¹ an / ci :: l after -Nbk'ihlcn on Uaumlcni | tci aiii: vciscl / l m.in with 4 : ' NalnumoViilai and xcinilii'i iinii'i' Stm.den. I lic i .11 hshifn .'- siniL 'then becomes duicl

21 OO 080

23

24

ιΙιι, ημιι Mim .uis'vsehiedciicu k iiplcni \ alal bright. ; .ίιΙι.ί I κ hlei. hlhcil iiiul> _ · 111 his very μηΚτ W

ItIIl ¹ I) I ΙΙκΙ.ΙΜφΓι'Μ ('del Spi iilllKK klK Π Crlliill HIiIII l'fllllK'il.

Ii dimkelbi, nines I ai hsUillpiiluT. the very lcichl in indelible I ahclk · siiul wcilcrc loaf

ι, ι ssi, · ι lnshiii lsi \ ul Hjuiiiwollc ei hall man in (ic aul; 'ciiihrl. die; m; ilujj ilen chcn; jcuebencn

, ■ MW.hi \ iiii \ ali uinuai bnnal odi'i Mali iumbicai hu- "■ play 4 ^l ) Ins s2 can be heal-eslelll.
al ι iihinlai Ivne I aihiini'en oiJci l) iueke mn be

McI, ill I .Ii hloTi .ml H.iumuolk

(U (Il S (IiI

SO, (I I (II. OSO.

ik-SL! l

IN SI ι (II ( ¹ II. OXI), H

ι it Il
I \

S (I (II III (ISl) I I

! \ S (i CU (Il (ISO I I

IClI
I \ S (I (Il (H (ISO Il

ι ii
OC II

i \ st ι (Il (Il OSO 11

■ κ Η

]

υ-, st ι (Il CU (iso.Il

ι I!
HN Sd. Ill, LIi, OSO ₁ H

NH.

SC). CH- CIi. C) SO ₁ H

NH.

K) ₁ S SO; CH, (. H. OSO ₁ H

COOH
11.N - - SC). CH, CTl, OSO ₁ II

NH,

HOOC

SO. CW ₂ CW. OSO ₁ H

(ll.ll.lV

Km

Km

K.H

hlinlslldll

Rm

RoI

roisiiehigc Onince

Orange

Rm

25th

Example \ / .. k. Ίΐιροικ-ιικ-

<> ll

26th

1., / ι> k <■ <11 1111> | ti Ί II '

s'> Ml Ml <) s <)

\ | I (I) {|| SI I

Ii, ιiim w

sll, hi

.lev I

11. \ mi (11 (Il ι is (ρ

S (ι Ml (Il (IM ι

11. \ (

Ml 11 pm

Wed || (

ι ill

'ι ι' '(Π ι isi ι 11

Hos

K (M III Il Si ι I I

'-. I I

'-, I I

M Ml (is (ι 11

Il (Il im

¹¹ M! Ml ι is <ι

, N SO. (H, CH, OSO, II

OCH,

SO, CM, (Ii., OSO.II (H,
OCII.

H, N SO, CH, CH, OSO ₁ H

OCH ₁
Cl

"- ^N " SO, - CH, - CH,

OSO ₁ H

Domesticated

rolsIichiL Or.msic

-ΐ * ν »'• er

/ Γ

11th

orlsCl / ΙΙΠίΙ

21 OO 080

28

ii ¹ ! \ / i ik «Hlipnili III ·

I) | .l / i> ki

I Ii him)

Hii unnu

(Il

ill--! ¹ !

MIi in I I. < 11 .si ι Il

S <l (Il (II. (ISi i.l I

Hi) .s

SO (Il CU, (ISOJ I

SI I ₁ (II. Ill OSO,

(<) (Μ I I I N SIl (Il (Il I) S (I

M <κ κ

SI I III (||. () S (>_; lI

si '(M CII. (iS (1 I I

\ ι) C

si ι Il

N Sl ι (I I, (II, () S (I

() ι. 111 υ c

ul-IIt.ii

S (I I I I III. OSO

II. \

KoI

I I N

ι. 1ί _: ι ISO ₁ I.

In Ruhr

Jcsg!

dcsel.

I, N 'SO, CH, CII, OSO ₁ II Cu blue «

Board

OH

H, N SO ₂ ClK-CH ₂ -OSO ₁ I! Cu

CH, OH

rolsi Viol

H ₂ N SO ₂ CH ₂ -CH, -OSO ₁ H

OCH,

Cu viol

2 1 OO 080 / IV

M)

¹¹ '^;'■■''■■''''

'. (1, H! Will MMh

n.llio-.i - aiii pll I ·. "· -'closl.

ii.iM, - ¹ ; Millaloalh! -. Um- ^1: ,: ii'hi! ·.>...;.; ■ '. ι mn '' Km MiN ₁ Xn \. < I / I mul ■ -ll.ni hu

H.uinili π pi ι aim m ~ '''>m'>'■■ a --ci inn ^: '! Mi \ ι-; ■ 1 la 11, - i ι <-aiii: ¹ uu. I m ι mi-. \ l ι si Ium- ¹ au <! 'μ hi

Ir ι π mc, 111 -.onailosima ¹ aiii pll '^ -. clo-u η u '. 'imii ¹ ''11-1 Ii I. IDU _: ·! is ι mil I .. ι: ι mi NaM> ciiuci uhi '

J ₁₁ \ ·, \ () Wl -ι'Ι / ¹ IU Ii; I IU,,; '' COW .ι. ii .Ul-- Μ ' ¹ . 11 Γ MlI ΐ ¹ > \ 1 Il 111! all CDI Ic: Π I lll.tll viii NlIl Il ΙίΙκ I -chill

JpIIi! 11 Ii ι ■ Ils uiiil I'm ;; " _η \, '.. ι> an- ¹ -, - im! -. ι.', ·. · ■ \ ππ.Ι · ι-ιιίΐοπ ..mi -. ■ Man" lh ¹ ο I \ lo

JIiJ ₁ [I ^ι · -, a, ■ h 1 "- ^. I at 11; μ 'M1! 11 η.' η !. ι u ι ί - ι)! I ¹ M ^ S U1! ο ί, μ · η 11> η \ ι j 11; ι π ι 'M 11 a ρ Ii 111 ο i ^ - u ί11 msa 1111

J ₁ IiU! ' an Nil ι il ■ ·,; i ί ν. ι - \ η '■. ■ ' ■ · '-π Hi ή--, ι ι η a / ιι ι Ii ι; . . iim <! K οι π μ a: ί h -. ■ · ■ hi- ί 11 ('l, ni "s.ini im! I, ι is'aih

pKi / .isiisncn-.ioii -ihi mm ¹ M \ U <'■ ~ . 'mI! o> .hi -icrn.jn N.ili mm ί,:. ml. aicn pll Wen from -1. '

λ, ,, n \ j., ι HI ₁ ;.,! ιι, ιρ'ιι 'ί ■>' ■ ^{; -ii:} i Ή-: m .- li'ii / II II in! his -4 .. Nail) l ·; .. a-ilci. · K 11 ppi im :. ¹ : 'il ^v man ^{; i} ' -

Jj ₁ -IIi.)]. · Ki isia !! i-ici Ii-H, '■' - ■ i! Uuiaa,.; ι Ιηί '! ¹ I- k; isiaiii-: ci ic -. ! ·, Upi.a -iiliai uiul M) ■ · k ι iviall'sici ic-

|| ι (!, !! -, - sam aU -.an ': i ρ! I v \. · γ \><·; \ ~ ·'", · 1 μη Na ¹ ; μ ma C-. la Ma- : .η- ι ;. ■ "| - ,;. ani-'c Sin πι U η am K π ι k

|) .ιΙκ · ι vcrnihil üian I ¹ -'- u. Κ, ι · μ:,; μ '^; a! M; - '; - Huh Iv- i! i- Mii.aia-i,; mh kupicluiiL ¹ ha.-u.lcl i-.l

C) cn cnisiainicncu i -n i'sioii. ^ Ίμ.: .. ί ^ι! 'ι aliuni after \! h. nlilcn .nil Κ, ΐιΐιιιίιΊΐιρ, -ι.ιΐιιι vm-.cI ,; mm

^ liloiii! air-! il'iii'il im · '- v \ a ». Ii:: ': m mn ■ s.'Jimm nn! '":.' Ν, ιΙγίιπιοχ.ιΙ.ι 'mi ·! IhIiii cima ^! In - ,! cn

Potassium cliloi iiilosim-- Π · ι! μ Ι η ί- ■. '. η mm '. , vum ^ν ! .ιη Μ., π \,>; _{: ι} au. -c-lhi -ilciicn K iipLVi. . \ ..!. U mn

^ ₁ -, -Il Sis (ill C '.X ¹ M i'il 111 "., I: -IaM CU ^1. ' ..MM- i-.i! .. ¹ I,! I: I ,; s 'a. il, icllcll k I i pll'! I-. Ί Il j ^:! ■ ■! a I ί "-1 ot

! ill hi.lli s i'liivcvda ;. saw there; \ *.: .. \: ■ ■ '■ ■■ ·''-s ¹ -'. !! .; ·. Jhm ,, mum.,; ,,; -.;, ,,, ',: ^ iiiniiin'- m; iü Man c-um

jj, l \ ui ilaiiniwiiilc cihaii iiMiian- aa, ι · i! · / M-: cm ImM ;, Wi -.- m 1, -, ¹ MhM- ih'i.iM! ¹ HiV--: 'mi

I ^- ) MKkPH- :, ¹ in (lc;: i'lv.arl ν > ¹ H Na !; a mi, Ιμ · μ ι 'μ ·:;., Ι Ha liin'.vo | I · id. -, I-'cm acM-i - c '! Ui, .- mIi.iI: m.iu π

n.iih n.iiiiplcn Ix-I HH (cclhsiiciHM'ianac ί)! π .. i ·. ·. ! ici: cnvvai! \ .- π Well! ι mniiii. ai i>, mi.iI "j,., N. Juun

Hin M ' ^: hi- schi silica M ¹ I ¹ Ih u,; ■ carbouai hiaiis'icii a \ iolclk ¹ laiinm; ¹ - ;; ühi ami

,1; \] ,. i 4- \ nimo -7 s - iimi.! ii-

In ilcr iolccPilcn IaK ¹ IU ¹ sun! vvcilcic loaf sloll · -.Γ'.κ'ίΓιΙΐΓΐ. ι! ic in, iii.'Iojm W cisi ·! icil-csuIIi wcn.lci

uiioi; \ i'x-n / o! w-

in omu vV .ism.- · um

OH

\ SO. CH, C ¹ H, OSO,

SO, H Nile

CO CiI, CH: SO, II

SO. CW. CIK OSO, I.

Ml,

orange

SO, CIl, C] I, - OSO. Il

iiitslichiucs Orancc

¹ '21 OO 080

31 32

OH

clull larbion on cotton

, ν SO (H, CII.OSOJl rolstichiiics

SO ₁ II NH

CO CW, CH. SO ₁ II

OCH,

SO, CH CH, OSO ₁ H RoI

ucsgl 11; N

C \\ _t
OCH,
_Λ ^ ₁ μ, _N SO. CH, CH. OSO ₁ H bhiu.licliiL!

OCH,
Cl

i, v SO, (II. CW, OSO ₁ II üL-lbsiichiü

ι! ι> μΙ. "- - -" Orange

ClI.
, ^ ₁ ,,, _N SO, CH-CH, OSO ₁ H orange

NH:
HC SO, CII, CW- OSOJl Orange

(Il'sL'I,

NH;

,!,. "" I IK) ₁ S SO; CW ₂ CH; OSO ₁ II orange

coon

I, N SO, CU, CII, OSO ₁ H lotslichiucs

Oiaiiiic

ι U- ·.!. ·! HOOC SO, CII, CII, OSO ₁ H iiilsliLhiu

SO, ClI, CW, OSO ₁ II

. 1ι · -.ιϊ1 II. \ OCH, rolstichi

SO ₁ H

, k ·., ·! 11, N SO, CH, CII, OSO ₁ H Oianuc

SO (| l, (Il () S (1.11

1 - I Il \ ι II ₁ 'li.ii.n ·

| o S (I, CII. (II. ι) S (I ₁ II (Ii Uiibiii

Oll

S (I, (Il (11, (ISO, 11 (η ιοΙΜιι, Ιιιμι

33

Continuation University:

M.spicl A / okomponenlc

Di.i / okompoiKTiIe

34

McI, ill

I'.irhlmi

H.IUIIlUi)]

OH

SO ₁ H

Nile

CO CII, CH, SO ₁ H

dcssil.

OH
Il _N SO, CH, CII, OSOJl Cu YuiliMi

CW,

OH
UM- SO, CH, - CW, OSOJI Cu hlausiichi

OCH.

Nile;

ICO SO. CW, CIl, OSOJI Cu ruby

OCIl,

I (, _N SO, CII, CH, OSOJI Cu rolslidi ^ c

^; "-...""" \ ioleli

of;:!.

OH

SOJI NII

CO CII, SO ₁ I OCII.,

II.N SO, CH, ClI, OSOJl Cu violen

CH ₁

II.N SO, (H, CII, OSOJI

iiclh.Mid-Oraiiuc

NII,

SO, CII, CII, OSO ₁ I

() i aiiüe

Nile,

SO, (II. CH, OSOJI

SO, CII. (II. OSO,

.! jelhsliehip orange

.l.-rl (K

M), (II, (Il OSO.

1 "IsIH lllsll"

(li.inco

lll-M'l

SO. (H. (11, OS (IJ

Ki.l

21 OO 080

35

orlset / ung

_L. "P, _L. | , \ / oliOiiip.iiienle

OH

SO ₁ II Nile

CO CH, SO ₁ II

ilcsul.

ilesul.

desul. 36

ilcsel.

dcsiil.

iloul.

ilestl.

ilcspl OCII,

HN SO, CII, CII, OSO ₁ II

OC H ₁

Cl
ΙΙ, Ν SO, CII, C]], OSO ₁ II

t'lli

ILN SO, CII CII. OSO ₁ H

Nile.

WS ' SO. CW, CH, OSO ₁ H

NH,

IK) ₁ S SO, CII, CII, OSO, Il

COOII

UN SO, CH, I'W, OSO ₁ II

Nile.,
IK) OC SO, CII, CH. OSO ₁ II

SO ₂ CII. CIL OSO ₁ II
ILN OCH.

SO ₁ II
ILN SO, CH, C]]. OSO ₁ II

SO, -CII, CII. OSOJ1 ILN CH ₁

Metal I-arhtun on cotton

hlaiiMichiiio Wedge

HO

IN

NII,

oll

SO, ClI, CiI, OSO ₁

orange

Oranuc

Orange

Oianuc

rolsliirhijics

Oraimc

orange

Red

Red

Red violet

SO. ("II. I

I, OSO ₁ II Cu violas

ilesul II. N

c ;, (II (II OSO ₁ II Cu

Violell

Fort set to η υ

1 .Ii htm! .mi H.iiii; '.'Ik-

OM

SO ₁ H
NII

CO CII, SO, M Oll

II, N SO, I'll. (II. OSOJI <ii r.'iMiiJiiJi-. Hi.iu

OCH,

Ml,

II.CO SO, CM, CII. OSOJ

OCM ₁

II. N SO. (Jl (Jl. (ISO.I

OCH ₁

H. \ so. cn cn. (iso.i

ι ii.
<K ii,

11.N SO. CM. (Il OSOJ

Cu

\ h'k-l

\ L-k-ll

iiilsli, i-: _L v Ul.Il

! 5 c i s ρ ι c I 141

0.1 IvIoI .V / Z-Sullaloäthylsulionylaniim was adjusted ^{to pH 6.5 at room temperature in 5 (1 cm x 1} water with 6 (1 cnv ¹ sodium carbonate solution) and dissolved, 20 cm ³ _{5N NaNO:} added and mixed from 125 cm · 2n-H ( ^1. K) Og His and 0.5 cnv 15n-NaNC), stirred in. After 15 minutes, the excess of nitrite is removed with a little amidosulphonic acid 0.1 mol of 1 -, / - sulfopropionylamino-S-naphthol-4-sulfonic acid and slowly adjusts the crystallized sodium acetate at 5 ° C. to a pH of 3.5 to 4 cm, stirring until the coupling is complete. The resulting dye is precipitated with potassium chloride, filtered and washed with 15% potassium chloride solution. It is dried in vacuo at 50 to 60 ° C. It is a red-brown powder. "Jas: is easily soluble in water. On cotton in the presence of sodium carbonate or sodium carbonate, bluish-red colorations with good lightness are obtained.

Example 142

I). I mol of 2-amino-4-, .'-sulfaioaihylsulfonylphenol become at 10 to 20 C m I 2> cnv ¹ 2n-lU'l with 20t.ni 'Sn-NaNO, dia / olicrt and the hot shoe of nitrile With a little Amidosullonsäuic destroyed / u dei Dia / oniumlösung one gives 0.1 mol 1 -,; - sulfopi · οριοη \ I-amino-K-naphlhol-4-siilli iiisäiire \ ιηό 211g crisp sodium acelal and sets ιίιιΙ lO'mmOmmoh a pl 1-W'eri from 7 to 7.5 a man verriihil at Kaumtenvpci atm. In the clutch ου ι,

is finished. Then 25 g of crystallized copper are added IersuH'at and 25 g of crystallized sodium acelal and stirred for 1 hour at 30 C until the cup ended isi. 2.5 g of sodium oxalate are then added and stirred for a few hours, filtered from the precipitated copper oxate and the l-'arhslofl from the Solution isolated by evaporation or spray drying. The dark brown powder is very easily soluble in water. From alginal thickened pask you get on cotton in the presence of Nalriumbiearbonal after usual steaming bluish-tinged red shades with good to very good imperfections.

Example 143

so 0.1 mol of 1 - amino - 2.5 - dimethoxy - 4 -; - Sulfatoäthvlsulfonylben / .ol are dissolved at 20 C 'in 50 eiiv ¹ water with 60 cm' ¹ sodium carbonate solution at pH 6.5 ^{, mixed with 20 cm 1} 5ii-NaN (), and in a mixture of 125 cnv ¹ 2ii-HCf, K ) Og His and 0.5 cm x ¹

ys 5n-NaNO, stirred in. Removed after 30 minutes one with elwas Amidosuli;) iisäure the überuli Nilril and gives 0.1 mol! - / »'- Sullopropionylamino-S-naphlhol-4-sulfonic acid to. The pH value is adjusted to 4 to 4.2 at 5 to K) C by slow

('1 / ugabe \ in crystallized sodium acelal em and \ erruhri thereby. In liie clutch end isi. Man \ now replaced with 30 g of ki islallisieiiem Kupl'ersulfai uiui 30 g knstallisierleni Nalriuinaeeiai and koehl a few hours at Rüekllul.i. until the copper img

(1 s is over. After cooling to Kauini tempera Im \ eisetzi man with 4.5 g of NaIi iunioxalal. Man IiI-tiierl from the excreted Kupfei oxalal and isolated the new K uplerkoiiiplexfarbslofl duieh im-

1 21 OO 080

39 40

Spray drying. A dark red-tinged blue is obtained, or prints with gi

liver, which is easily soluble in water. I personal property.

The following table contains further dyeings

iumcarbonal or Natriunibicai honal which can be prepared in an analogous manner

\ /> ik> HU | Ίι ΊΗ-Π U- I > l.l / t ik ι Ml IP * MlcnlV Mcklll I ■ iublt Hl il

H.iumuolle

II. \ S (I. CII, (II. OSO ₁ II Km

S (I CII. CII. OSO ₁ II hLiusln.-hi.ui:

II. \ SO. (II. CII, (ISOJI

SO. CII. (H, (ISO, 1

O (Il

, Irs-i II \ S (I. (H, (II. OSO ₁ II Vuili-ii

Ol 1I ₁

j ι

. '. ■ .--. ■ • ι II ¹ -. S (). (II, (II. OS (i.ll RoI

<Ii
Λ · ... ·! I ¹ N Si ι ι. 11. CII OSO.11 Ro!

NH,
dcsi; l. H ₁ C- "SO, CH, CU ₂ OSO ₁ H RoI

SO ₁ H
the same. H, N -. ' - SO ₂ -CH ₂ -CH ₂ -OSO ₁ H red

NH,
the same. HO ₁ S - - SO, -CH ₂ - CH, - OSO ₁ H red

COOH
de «.;!. H ₂ N- -SO, CH, CH _{2 -OSO 1} H RoI

Il

41

42

Kortsel / ung

example

Λ / .ikompoiHMile Diii / nkoMipnia-nU

HO Ml (O Oil, (M, S (ι, ΙΙ Nil.

< IKHK s (i. (H, Cl I. (ISO, Il

Mi-I.ill l ^; .nhl B.iuni

so. (II. CII, OSO, Il

I N (KII, hl.ms

Si I CII. (II. OS (ι, ΙΙ

II. N (II, KnI

on

IA SO. (II, (II, (IS (1,1 I (Ii Vmk

II.N

S (). (II, (II, (IS (I, Il <π

II 'ι Ml (

SO, H

ties t!

H, St. Vi.ill. ·

I'l

on

II.N

Ml, (II. (||. (ISO, Il (Ii 11 Mi ..

SOYI

oh,

Ml.
Il ((ι S <I. ill. (II. OS (I ₁ H (U

(K II.
II.NS () CII (II. OS '), ll (Ii

οι π,

I.N SO. (||. (Il OSI 1,11 (Il

'n.

Il N SO, CII I'll. OSO Il

NH,

SO, CU ₂ - CH, OSO ₁ H

Η, Ν · ^: --SO, -CH, -CH, -OSOJI

NH, H ₁ CO- SO ₂ -CH ₃ -CHj-OSOjH

(XH ₁
Η, Ν · -: '''- SO, CH ₂ -CH, - OSO ₁ H

hiatis vliik-

Red RoI

blue bl.iiis

ortset / .uiiti

43

A / iikiiinpiiiii-nli. ·

IK) Nile (O (II. Si I ₁ II

SO ₁ II

, Ιι, -sL ·!

21 OO 080

44

I n.i / i'k'unpnni-nu-

(HII,
H, \ so (II, CII, OSO ₁ II

111

οι ii,

II, N SO. (II, (II, OSO ₁ II

Μι-lull l-'iirblim -ιnt Haunmolk

hlaiKlichii-i-s RoI

violet

(Ί
H, \ SO. (II. (II, OSOJI Rcil

<Μ,

II. \ S ( ). (II, (H, OSO ₁ II Rn!

Nile,
III SO. ("II (II., OSO ₁ II RoI

Nile.
HO _; S SO (II. (II, OSO ₁ II KoI

SO Il

IiN SI) _ CII., (II .. OSO ₁ II Hi «

Nile

SO (II. (II. OSO ₁ II

Red

descl.

the same

the same

the same

dcsül

II, N SO, (II, CU, OSO ₁ II

SO. (II, (II. OSO ₁ II

", N OCH ₁

S () _: CH ₂ CH ₂ -OSO ₁ H

H ₂ N - ', "- CH ₁
NH,

RoI

Red

HO ~ f SO, -CH, CH ₂ -OSO ₁ H Cu red violet

OH

H, N-Γ -SO ₂ -CH ₂ -CH ₂ -OSO ₁ H Cu violen

OH

H ₂ N - f - SO, ~ CH, -CH ₁ -OSO ₁ H Cu bluish tint

= - '"' Vil

CH ₁

violet

21 OO 080

I ortsct / unu

(i Ml ('ι (I I s ι. i!

1, ill'Mll ill
H.min. '..' lh

IM III (ι, I. I- I. Ιιΐ'Ί

¹ ISI 1 I j I., R,

H e ι s ρ ι e i 1 ν.ι

0.1 MoI · -., - () \ alh \ Ku! F'i '\! Ai!';, - .v- ": τ 125 cm '2n-s.il/acid and 1OH. · ■ -"" .ί 21 'a Sn-NaNl). ..lia / otiert. Dei "l"' is called si_hui ^; :: · Ni; ii ■. ·. ι: 11 but some Amidosulfonsiiinc eii'fcinl. / \ · de; eil .. · ,! ¹ tcnen I) ia / oniumsal / solution is then added nl V:> 2 Sulloaeei \ lamme- 5 - naphthol - 7, '!!, psjiv ;. ι; _· ,: stelll at Ο to IH (by / envi iiliopkn: - .w ι; Natriumacelatlösung the pli-Wcr au \ n>.!.! ■ - !. da After completion kuppluiiL 'i' ill 'is nevertheless "■. siandctien dye mn NaIi luniehloi; d, in ". Irin- :: um! washes it with 20"., 1PeI Naipumchlondliisun · and dries it in a vacuum from 50 to inn ('"('in 250 l: concentrated sulfuric acid and until / ui \ ollslandiL. ^T en solution at 2n to 2 ^ς (\ eiriihrl Neutralized at 25 to 35 C with sodium carbonate to a pH of 4.5 to 5.5 by adding sodium chloride the dye is deposited. filtered and washed with saturated sodium chloride solution. After drying in vacuo at 50 to 60 ° C., an orange-brown powder which is identical to the dye obtainable according to Example 1 is obtained.

In a similar way the above listed metal-free dyes are produced.

Example 190

0.1 mol of 4 - . '· - Oxäthylsulfonylaniün are diazotized in 1125 of ³ 2N sulfuric acid and 100 g of ice with 20 cm' of 5N NaNO ₂ . The excess nitrite is removed with a little xmidosulfonic acid. Now you give t) .l mol 2 -,; - Su] fopropionylamino-5-naphthol-7-sull'iiiN.iiii, / w lind -uvl Ιι ..- Mibis Ii) ('through / iHmplen "!'. a '.Wi!'! L'icii Nairiiimacct.itliisun.L ¹ aiii a pH - \\.-π μι! f.η to 4.0 a After bccndclci kuppliiii :;! Miller! in, in ilen originated Farhsmll dii'cli Spi,: l'jti->cl> tuiiiL '.'del I indaniplcii. 50; j des trekkeilen I .Ii' ¹ ^. 'Me- one solves in the 4fach.cn (icwich'.s -. (' MeüLii ki-ii ■■. ■ !! ',! i -.' i let Schw ele'saure at 2l) Ins 2 ^% 'C and iiiliii oieselösiiiij on MK) v? l-is "and neutrahsien the St h wck Kau ; · ■ at 2 ^ to 35 (nut Natiium-.atbiinai b'N / u emciii pH-'Acri of 4.5 b; s 5. ^ Del I arbstiill is then mn sodium chloride \ olKtandiL.: - abu'c - cliicdcn ablüiricil and gesätligtci N.tiriuni - (1 '1-'1'IdIoNiIiVj washed After Irnckncn in N'.ikasi'i at 5-n hi »H...) C. erhall a Farhstofi -.ier;. - . '! the idcntiscl lsi available after Ucispie; \ ~.

^ · In al ".n! Ichci 'Ά the above-mentioned! Metallirecn \ arbslolle can be produced.

Example 191

0.1 mole of 2-amino-4 ,; - Oxyäthylsulfonylpheno are diazotized in '25cm' Zn-sulfuric acid and 100g egg with 20 cm ³ Sn-NaNO ₂ . The excess of nitrite is removed with a little sulfamic acid. After adding 0.1 mol of 2-sulfoacetylamino

5-naphthol-7-sulfonic acid is adjusted to a pH of 8 to 9 with sodium carbonate solution After the coupling has ended, 25 g of crystallized copper sulfate are added and 30 g of crystalline are added Sodium Acetate. The mixture is stirred for 1 hour

6s excretes the copper complex pigment with cooking saline. filtered and washed with saturated table salt solution and then dry it in a vacuum at 50 to 100 ° C. 50 g of the dried dye

-Sfc.

21 OO

are added to a mixture of 200 g of monohydrate and 300 g of o-dichlorobenzene at 20 to 25 C and stir overnight at room temperature. This mixture is then stirred on 600 g of ice and then neutralized with 200 g of calcium carbonate to a pH of 4.5 to 5.0. The mixture is heated to 70 to 75 ^° C. for 30 minutes, filtered hot and washed with about 1 liter of hot water. The filtrate is saturated with potassium chloride and the precipitated dye is filtered off and washed with saturated potassium chloride solution. After drying, in vacuo At 50 to 60 ° C., the same dye is obtained as described in Example 33. The other copper complex dyes of Examples 34 to 40, 68 to 70, 86 to 89, 110 to 113, 133 to 136, 159 to 161 and 181 can be prepared in a similar manner to manufacture 184.

Example 192

0.1 mole of 2 - amino - 4 -, -; - Oxäthylsulfonylphenol are diazotized in 125 cm ^{3 of} 2N hydrochloric acid and 100 g of ice with 20 cm ^{3 of} Sn-NaNO ₂ . The excess nitrite is removed with a little sulfamic acid. After adding 0.1 mol of 2-sulfoacetylamino-5-naphthol-7-sulfonic acid, the pH is adjusted to 8 to 9 with sodium carbonate solution. After coupling is complete, the pH is adjusted to 2.5 with 2N hydrochloric acid and the uncoppered dyestuff is precipitated with sodium chloride, filtered and washed with a little saturated sodium chloride solution and dried in vacuo at 80 to 100.degree. C. 50 g of the dried dyestuff are at 20-25.degree added to a mixture of 200 g of monohydrate and 300 g of o-dichlorobenzene and stirred overnight at room temperature. This mixture is stirred on 600 g of ice, 12.5 g of crystallized copper sulfate are added and the mixture is neutralized with calcium carbonate to a pH of 4.5 to 5.0. The suspension is heated to 70 to 75 ° C. for 30 minutes, filtered hot and washed with hot water. The red filtrate can, as indicated in Example 191, be gelatinized with potassium chloride, or the water is evaporated by drying or spray drying. The dye obtained is identical to the dyes obtainable according to Example 33 or 191.

The dyes of Examples 34 to 40, 68 to 70, 86 to 89, 110 to 113, 133-136, 159-161, and 181-184 will.

Example 193

0.1 mol of 2-amino-4 -, - oxäthylsulfonylanisol are diazotized at 5 to IOC in 125 cm ^{3 of} 2N hydrochloric acid with 20 cm ^{3 of} Sn-NaNO ₂ . After removing the excess nitrite with about sulfamic acid, 0.1 mol of 2-sulfoacetylamino-5-naphthol-7-sulfonic acid is added and the pH is adjusted to 4.0 to 4.5 with crystallized sodium acetate. After the coupling has ended, the dye obtained is precipitated with sodium chloride. filter it off and wash it with about 20% sodium chloride solution. The moist dye is ^{stirred into 100 cm 3 of} water, and 25 g of crystallized copper sulfate and 30 g of crystallized sodium acelai are added. After adding 25 cm ^{3 of} pyridine, the mixture is refluxed for a few hours until the dealkylating coppering has ended. The resulting copper complex dye is deposited with sodium chloride, filtered off, washed with saturated sodium chloride solution and dried at 80 to 100 ° C. in vacuo. 50 g of the dried dye are introduced into a mixture of 200 g of concentrated sulfuric acid and 3 (X) g of o-dichlorobenzene at 20 to 25 ° C. and stirred overnight at room temperature. This mixture is stirred on 600 g of ice and then neutralized with calcium carbonate to a pH of 4.5 to 5. The resulting mixture is then _{heated for 2} hours at 70 to 75 ° C., filtered hot and the calcium sulfate with about 1 liter of hot water washed out. The red filtrate obtained in this way is either mixed with potassium chloride, the copper complex dye separating out as the potassium salt and being recovered by filtration, or the dye is isolated from the solution by evaporation or spraying.

The same dye as in the examples is obtained in this way 33, 41, 191 and 192.

Similarly, the dyes of the examples 42 to 48.90 to 92, 94, 114 to 116, 137 to 140.

143, 162 to 164 and 186 to 188.

65 parts of the dye of the Frrmcl

example

HO ₁ S II, C "OC UN

N ■ - ■ · N

SO, ClI, CH, OH

(Obtained according to Example 191. Part I or Example 193, Part 1) are heated to XO C in 400 parts of pyridine. W) parts of sulfamic acid are then added in portions one. where the temperature Ins 105 C: insieii! t. The mixture is stirred for 30 minutes at 105 ° C. and distilled then 300 parts of pyridine in vacuo. so 30 parts of water are added three times and 30 parts of distillate are distilled off each time. Then it will be 700 parts of water are added to the residue and about 20 parts of nalruimbicurbonal are added to one

609 630/113

⁴⁹ , ,, _n , η dyes identical. In a similar way

pH adjusted from 5 to 5.5. The obtained red "halunun ^ - _{dcr Bdspiclc 42 to 4} 8. 90 his

Solution will be clarified. The dye can now be removed. ^ ^ ^ ^. ^ ^ _{) 62 bjs {M} ^

neither by folding with potassium chloride nor by ν - _{hcri: cstc} in

Evaporation or spraying are isolated. He is 1S6 to ISh only _e

with those according to Examples 33, 41, 191, 192 and 193 5.

Claims (3)

21 OO 080 Patent claims:
Water-soluble monoazo dyes of the formula OH X As. \ - vX RN 'S (X-CH ₂ -CH ₂ -O-SO ₁ H CO-CII ₂ - (CH ₂ I _n -SO ₁ H in which R is a hydrogen atom or an alk}! group with 1 to 4 carbon atoms. X is a hydrogen atom or a hydroxyl, melhoxy, ethoxy, carboxyl or sulfonic acid group, Y is a hydrogen atom or a methyl group. Ethyl-. Methoxy-. Ethoxy or sulfonic acid group and η denotes 0 or 1, and their copper complex compounds of the formula Cu ho, s -; ~ --f V ^N = N-- ^; V - γ RN SO ₁ -CH ₁ -CH ₁ -O- SO ₁ H CO -CH ₂ - (CH ₂ ), - SO ₁ H in which R. Y and η have the meanings given above. 2. Process / ur preparation of water-soluble reactive monoazo dyes of the formula OH X X / V \ X RN SO ₂ -CH ₂ -CH ₂ -O-SO ₁ H CO-CH ₂ - (CH ₂ I _n -SO ₁ H in which R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a hydrogen atom or cine hydroxyl, methoxy. Ethoxy. Carboxyl or sulfonic acid group. Y is hydrogen or methyl, ethyl, methoxy. Ethoxy or sulfonic acid group and ir is O or 1, and their copper complex dyes of the formula 2 Cu O O . ¹ I, HO ₁ S ■ ^: ■ { ^NN ij Y (2 | RN SO, CII ₂ CH, O SO ₁ H CO CH ₂ ICII ₂ I ,, SO ₁ II in which R. X. Y and // have the abovementioned Haleiithm, as well as procedures / u their I must be created. 21 OO aby üekenn / cichnol. dal.i man al em amine of formula 3 SO ₂ CW ₂ CH ₁ O SO ₁ II η which X and Y have the above-mentioned conditions have, dia / otierl and with a Λ / ο- is Component of Formula 4 11O ₃ S--! I ^; (4, R N CO CW ₂ ICH ₂ ) ,, SO ₁ II couples, where R and η have the meanings mentioned above, and optionally if X is a hydrogen alom or a hydroxyl. In the case of X = Hm, methoxy or ethoxy group means the presence of hydrogen peroxide with copper-releasing agents or b) an amine of the formula 5 have meanings, dia / oliert. mn a Λ / o component of formula 6 OH HO ₁ S -ij '161 R N CO CH ₂ ICH ₂ I ₁₁ SO., H in which R and η have the meanings given above, couples and converts the, / - Oxyäthylsulfongruppe into the /, '- Sulfaloathylsulfonylgruppc and optionally if X is a hydrogen atom or a hydroxyl, methoxy or ethoxy group - in the case of X = H Reacts with copper-releasing agents in the presence of Hydroxide or
c) an amine of formula 7 H ₁ N SO ₁ CW, CIK Ol in which Y has the meanings given above and X is a hydrogen atom or a Wy ilrowl-. Methoxy or alhoxy group. dia / oliert, with an A / okomponenle of the formula X. OH 40 SO, CW, CH ₁ OH in which X and Y are the aforementioned Be-I10, S -I
RN CO CH ₂ (Cl I ₂ ) ,, - SO.,! I. in which R and η have the meanings given above, couples the cold dye of formula 9 on RN SO ₁ CH ₂ CII ₂ -OH CO CH ₂ (CH ₁ ) ,, SO., I treated with a copper-releasing agent and the obtained copper complex larbstoll. j'cgebenenliills in (presence of organic solvents, into the corresponding sulfuric acid ester 3. Use of the mentioned in claim 1! dyes / around dyeing or hatchet of naliven or regenerated (ellulose fiber materials. wool, silk or! '(ilyamidl'asermalcrialien.