DE2022085A1 - Asymmetrical 1: 2 chromium complex azo dyes without water-solubilizing sulfonic acid or carboxylic acid groups - Google Patents

Description

FARBWEPJiE HOECHST AG 'formerly Meister Lucius & Ertlnini-c

File number

- JIOE 70 / Γ 072

Frankfurt (Main) -Hoechst, May 4th 1970 Dr Mü / B

· '■' · :; ': Asymmetrical 1: 2 chromium complex azo compounds jvas_s_crlöslichiiiachcnde sulfonic acid or carboxylic acid groups

The present invention relates to new, nitrogen-containing for fast dyeing natural or synthetic fibers unsymmetrical 1: 2 chromium complex azo dyes of the general kind Formula 1)

A-N = N-B

(D

^S0 2 ^Z) n

wherein A is the residue of a diazo component of the benzene or naphthalene series, for example by chlorine atoms and / or lower alkyl groups, such as methyl or ethyl groups, methoxy or nitro groups or groups of the formulas -SOpN (R) ,. or -CON (R ^, where ° R is a hydrogen atom and / or an alkyl group with 1 to 4 carbon atoms, can be substituted, B the remainder of an azo component of the naphthalene, pyrazolone or Acetoacotarylamid series, for example by chlorine atoms and / or methyl, methoxy, nitro or sulfonamide groups' may be substituted, C is the radical of a diazo component of the benzene series, which is represented by the group -SOpZ and / or, for example Chlorine or bromine atoms and / or methyl, methoxy or nitro »groups can be substituted, D the remainder of an azo component

109850/1432 BATH ORIGINAL

the naphthalene, pyrazolone or acetoacetarylanidreiho, dor by the group -SOpZ and / or, for example, chloratoinc and / or methyl, methoxy, acetylamino, nitro, or the group of the formula -SO _? N (R) ", in which R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, can be substituted, mean, X and X ^f for -0-, -COO-, Y and Y 'for -0-, -NH -, Z for the group

CH = CEL

(2)

or

- CH ₂ - OSO ₃ H (3)

and η stand for the number 1, and a process for their preparation, characterized in that 1: 1 chromium complex azo dyes of the general formula (4)

A-N = N-B Y

ion

Anion!

(4)

wherein A, B, X and Y have the meanings given above, and [anion] "for a non-complex-forming anion, such as a nitrate, sulfate, formate or Acetation, but especially a chloride ion, with complex-forming Monoazo dyes of the general formula (5)

/ ^H

X '
CN =

(5)

(Sun ₂ Z) _n

wherein C, D, Z, X ', Y' and η have the meanings given above have, in water or mixtures of water with water-miscible organic solvents such as acetone, alcohol or ethylene glycol, at pH values between about 4.5 and 7.0 at temperatures between about 80 and 120 ° C. in the presence acid-binding agents, such as alkali acetate, carbonate or hydroxide.

109850 /, U32 8AD ORIGINAt

Bio asymmetrical 1: 2-CUro3nkn: r, plc?: Azoj arusto.i. The general formula (1) with the grouping ~ CIl ₀ -Πί ,, .- öSO ^ II T-for Z ■ can also be so horgostcl.lt that nan 1: l-Chrorakoririj ox- · a ζ οι arbs.t of f ο of the named all; vemei lien V ornel (· ΐ ). with co ^ forming monoazo dyes from the general formula (5 a)

X ¹ Υ C - N = - N - D

SO ₂ -CH ₂ -CIi ₂ -OH (5 a)

according to the above-mentioned conditions to the 1: 2-chroa;

complete ex az of arbst of fen of the mentioned allr.onicincn Formol (1) · with the grouping -CH ₀ -CH ₀ -OH for Z _: uns.ptzt, and then g with conc. Schv.-ef clic acid or amidosulphanic acid / pyi-idin carries out the esterification to the group Z = -CH, - _{CH o -0S0 o} H. By treating with alkaline compounds such as alkali carbonate or alkali hydroxide, the corresponding dyes with the group -CH = CH ₂ for Z can be produced therefrom.

The process used as starting compounds l: l-Chromium complex azo dyes of the aforementioned all-one formulas (4) are obtained by heating azo dyes of the formula (6)

to 100 to 130 C in aqueous organic or organic Medium, such as n-butanol or ethylene glycol, with equivalent amounts of a chromium donor such as Chromium dlD chloride, chromium chloride acetate or formate obtained. For the production of the mentioned 1: J-ChiOmkomplexazof ai'stoff e suitable chromium (III) compounds are also obtained by reducing alkali chromate in n-butanol or ethylene glycol, or Mixtures of both in the presence of conc. Hydrochloric acid, whose Amount is such that the molar ratio of alkali chromate to hydrogen chloride 1; 4 is.

109850/1432

The nine 1: 2 ~ Chr οτΛ cn-] Λ (% -} :: \: η dyes available according to the vehicle are suitable for dyeing and printing β ticks tr,: - "Γ ~ containing fibers and fabrics, both natural and also of synthetic origin, such as silk, wool, polyamide and polyurethane fibers. The use of the new J, 'ctall.] »o; .'-, plc;: - azo dyes is carried out according to the dyeing and printing processes commonly used in technology .

For dyeing nitrogen-containing fiber material, the new metal complex dyes of the above formula (1) with the grouping -CH = CH ₂ for Z are distributed in water with anionic or nonionic dispersants or mixtures thereof and in the form of the aqueous dispersion or the powder form obtainable therefrom by evaporation of the water, or the dyes of the formula (1) with the grouping -CH ₀ -CH ₀ -OSOoH for Z, which are water-soluble, in the presence of anionic or nonionic dispersants or mixtures thereof, the weight ratio of dye to dispersant 1: 0.1 to 1: 2, placed in a neutral or weakly acidic bath of constant or practically constant pH and therein preferably at 70 ° to 120 ° C in the presence of compounds containing nitrogen for dyeing Textile materials are common, such as ammonium acetate, quaternary ammonium salts, colored. The pH of the dyebath can also be changed during the dyeing process by adding acid or acidic salts or alkaline agents or alkaline salts, for example in such a way that the dyeing process starts at pH = 4.5 and during the dyeing process to 8.5 elevated.

The 1: 2 chromium complex azo dyes prepared according to the process have gray, navy blue, purple, brown, olive green, red, orange and yellow hues. They show excellent affinity to nitrogen-containing natural or synthetic fiber materials and result in dyeings with very good light and wet fastness properties. Compared to dyes without fiber-reactive Groups distinguish the new dyes by better wet fastness properties.

The following examples explain the manufacturing process,

109850 / U32

Example I.

39.6 parts by weight of the 1: 1 chroynkoin plex dye of the formula

Cl "

37.4 parts by weight of the monoazof dye of the formula ^; . ■■ ■. ■■ - -. '■■' ■■ * ■ ^{: r} ''^; - ho :. . :: ν ..

OH

NaO ₃ SO-.

N * Ν— ¹

55.0 parts by weight of crystallized sodium acetate, 1000 volume * - divide water and 500 volumes of alcohol -will divide 5 hours Stirring heated to reflux. The alcohol is then distilled off and the l ^ -Chrome complex azo dye of the formula

NaO ₃ SO-H ₂ CH ₂ CO ₂ S

109850/4 432

Salted from the solution by adding 100 g of sodium chloride and the precipitate is filtered off.

The dye results on wool from an aqueous bath at boiling temperature, the pH value adjusted to 5.0 at the start of the dyeing process and towards the end after absorption of the dye is briefly increased to pH = 8.5, lightfast and washfast navy blue colorations.

Example 2

42.5 parts by weight of the Irl-Chroro complex azo dye of the formula

Cl "

41.2 parts by weight of the monoazo dye of the formula

OH

CH = CH,

and 55.0 parts by weight of crystallized sodium acetate «ground in a mixture of 1,000 parts by volume of water and 500 parts by volume Alcohol heated to reflux for 6 hours. After the alcohol has been distilled off, the dyestuff which has crystallized out is filtered off and washed salt-free with water. A dark brown dye powder is obtained, which with the help of anion-active and / or nonionic dispersants finely divided in water is and in the form of the aqueous dispersion or as a powder,

109850/1432.

BADORiölWÄi.

which by evaporation or spray drying of this dispersion is obtained for dyeing polyamide fiber material γ, -ird is used from aqueous, weakly acidic dye damage. Ilan receives yellowish red dyeings with very high light and wet fastness properties. The dye obtained corresponds to the 'formula

Na ⁺

Example 3

, 6 parts by weight of the 1: 1 chromium complex azo dye of the formula

K = N -

r ν ^

ο Y ^ ο

Cr +

109850 / U32 BAD

and 47.4 parts by weight of the monoazo dye of the formula

HO

are in a mixture of 1,000 parts by volume of water and 600 parts by volume of acetone heated under reflux with stirring, at the same time the pH value with 10 percent by weight Caustic soda is kept in the range 5.5 - 6.0. After 6 hours, the mixture is cooled to 50 ° C. and the pH is adjusted with 10% sodium hydroxide solution to 12.0 and after 4 minutes with 2 η hydrochloric acid back to 6.5. After the acetone has been distilled off, the crystallized precipitate and dried. The obtained dye of the formula

N / A

corresponds to, produces on wool from a weakly acidic aqueous dispersion reddish-tinged gray colorations with very good light- and wet fastness properties.

109850 / H32

BATH

39.6 parts by weight of the 1: 1 chromium complex azo dye of the formula

Cl "

and 42.9 parts by weight of the monoazo dye of the formula

HO

CH ₀ OH

■ together with 55.0 parts by weight of sodium acetate crystalline. heated under reflux for 6 hours in 1000 parts by volume of water and 500 parts by volume of alcohol. After the alcohol has been distilled off with 5 % sodium chloride, based on the volume of the liquid, the 1: 2-chromium complex monoazo dye is precipitated, filtered off with suction and dried. The dry dye powder is introduced into three times the amount by weight of 96% strength sulfuric acid and stirred at Rainntcmperatur for 3 hours. It is then poured into 1,000 parts by weight of ice with stirring, neutralized with alkali and the precipitated dye is filtered off with suction. The dye thus obtained corresponds to the formula

109850/1432

NaO ₀ SO-H ₀ CH ₀ C

Na ⁺

Dyed on wool from an aqueous bath at boiling water temperature, the The pH of the dyebath is initially set at 5.0 and, after the dye has been absorbed, it is brought to 8.0 to 8.5 for a short time one obtains a black ^ coloration with very good light and wet fastness properties.

Example 5

43.05 parts by weight of the 1: 1 chroma complex azo dye of the formula

Cl "

10985 0- / 1432

BATH ORIGINAL

and 43.0 parts by weight of the monoazo dye of the formula

COOH

are tind in a mixture of 1,000 volume η parts of water 600 parts by volume of alcohol with stirring for 3 hours under reflux heated, at the same time the pH with soda at 6.5 to 7.5 is held. After the alcohol has been distilled off, the dyestuff which has crystallized out is filtered off, washed and dried. The dry dye powder is dissolved in 400 parts by volume of pyridine heated to 80 C and with 60 major parts amidosulphonic acid offset. After 1/2 hour of stirring at 105 ° to 110 ° C, the Pyridine is distilled off, the residue is taken up in 400 parts by volume of water and 300 parts by volume of acetone, heated to 50 ° C. and the pH of the solution is adjusted to 12.0 with sodium hydroxide solution. After 4 minutes, dilute hydrochloric acid is added until the has adjusted pH 6.0. The acetone is distilled off and the crystallized dye of the formula

Cl

N / A

10 9 8 50/1432 BADORIGlNAt

filtered off. The one with the dye on polyamide fiber The olive-green coloration obtained from a weakly acidic aqueous dispersion has very good light and wet fastness properties.

The following table contains further examples that are based on the Procedures of Examples 1-5 were prepared.

109850 / H32

In the case of a monoazo dye, a Kowplexbildcnder MwW * - TOrol.

Talking game - the forrael (6), azoi agent the all ge on Yfolle

No.. "" -Which as l: l ~ Cr ~ Com- corresponds to formula (5)

_ plex inserted v / ird ^

OH

OH

ho cn,

- = N ~ C

eoiTH

Brown

OSO ₃ H

N = H

yellow-brown

CH = CH _r

HO CH ₀ Ii f ^H 3 \ ■ s 3
T \ OH ^ C ^X ^^ '^ s-N = N-C-CONH-f I yellow ) I. ² CH

OH

f ^H

reddish yellow

OSO

109850/1432

At- Honoaj'.oi'arbstof: C, rnt- cor.iple; r image <mder mono-

according to the formula (6), azo dye of the alIge

No. which corresponds to 1: 1-Cr-Com- my Forjuel (5)

plox is used. speaking

hue

on

Wool

OH

N = N-

NO,

HOOC

HO

OCH

CQlTH

yellow-brown

CII-CII,

HO

HO

V> —NO ₀
_ / 2

Red

OH

HO

N = N

H "C

CH ₂ -OSO ₃ H

orange

HO

13 cl

-N = N

OCH,

navy blue

OH

14 O ₂ N

N-N

HO

, -N = N-

V
HC

- SO.

CH ₀ CH ₀ OSOoII

olive green

109 8 507 U3

^BATH MM

At- Mofi'iazrofarbfilofj ', ent- KoT-vnlorbildrMidcr I'ono- color tone

play spx ^- echond of formula (6), azo camouflage fabric of allrc'c; - on

No. ^ clchr.v as 1: 1-Cr-Kow- mcinon Formal (5) ent- wool

15th

bordo

tn

f 17 18

Brown

bordo

Brown

19th

N = N

orange

109850/1432

ί * i / l. ■ '■ ". · - ■

Bod «Monoa ^ of arbstoi'f, ent- grain ρ In ;; V-.! Miserable;. '> ■:'; -. Fr-vbion

game speaking der- formula (6), nzoxarb: .- Ld'.C der πϋ / Ό- p.uf

■ No. which as 1: 1 Cr grain mean Γηΐ'καΐ (5) ent- ^τ , '.' * ..! 1ί ·

plex is used. speaking

HOOC

H ₂ K OCH ₃

dark «blue

23

NO

black

navy blue

24

Brown

109850 / U.3 2

BATH ORIGINAL

Bei- T.'onoazof arostof f, ent- KoinTJlexbild ^ riclcr mono-hue npiel surrciicnd cifir form ': !! (6), az; j.rai: bstrj: i'f der allpe- on no. Which as 1: l-Cr-ir ^ ni- mpinoii formula (5) ent- wool ρlex_jp> i_nrr os et ζt _v / ird ._ snrrchcod

HO.

V "

N = N-C

CONIi

OCH

-N-N-C

CII ₀ -CH ₀ -OSOoH

yellow

- Cl

26 i

Brown

- N = N

23 fi

HO

ΤΓΓ

violet

yellow

CH = CH,

109850/1432 8AD ORIGINAL

Claims (1)

P Λ T E N TANSPR Ü C II F. 1) Asymmetrical 1: 2-Chromkor'.p] cxazof arbstof fe of the general formula (1) A-N = N-B (D wherein A is the residue of a diazo component of the benzene or naphthalene series, which is replaced by chlorine atoms and / or lower alkyl groups, methoxy or nitro groups or groups of the formulas -SO ₂ N (R ^ or -CON (R) ₂ , where R is a hydrogen atom and / or denotes an alkyl group with 1 to 4 carbon atoms, can be substituted, B the radical of an azo component of the naphthalene, pyrazolone or acetoacetarylamide series, which can be substituted by chlorine atoms and / or methyl, methoxy, nitro or sulfonyl groups, C the remainder of a diazo component of the benzene series, which _{can be substituted by the group -SO 0} Z and / or chlorine or bromine atoms and / or methyl, methoxy * or nitro groups, D the remainder of an azo component of the naphthalene, pyrazolone or acetoacetaryiamide series , by the group -SO ₃ Z and / or chlorine atoms and / or methyl, methoxy, acetylamino, nitro groups or the group of the formula -SO ₂ N (R) ₂ , wherein R is a hydrogen of fat oin or an alkyl group mi t represents 1 to 4 carbon atoms, can be substituted, mean, X and X * for -0-, -COD-, Y and Y * for -0-, -NHi-, Z for the group "." ■ -.- "^Λ; - \. ". _: v- _: -..- :. ^: .; -. -) ///: ''-.-;'" .- desolate - CH ₂ -OSO ₃ H (3) and η stand for the number 1. 109860/1432 BATH 2> 1: 2-ChroMlvomplexXa.rb.stof f of the formula OSO ₃ H Η ^Ί 3) 1: 2 chromium complex azo color of the formula BATH 4) 1: 2 ~ Chronkoinplexa co-dye of the formula 5) 1: 2- the formula SO ₂ -CII = CH ₂ 1 0 9 8 5 0 / U 3 2 BATH 6) 1: 2 ~ Chronikomple;: aEof arbs toff of the formula 7) 1: 2 Chromkoniple3i: azo dye of the formula O ₂ N N = N OC N = N - χ I SO : iI = CH _r Y = - N.
^H 3 ^C 109850 / U32 tx 8) 1: 2 chron complex azo dye of the formula 9) 1: 2 chromium complex azo dye of the formula H ₀ C Cl N = N- V O \, 0 -Cr ' O / O OC / T-CH, Cl N = SUN ₉ I ² CH = CIL ι- * CONH 1098S0 / U32 BAD 10) Ancestors to the Ilerstcllum; un. 1: 2-chromium-complex azo dye of the general formula (1) 2022Q85 s vrcr.re t r i s cn e r Cl) - wherein A is the radical ^^ of a diazo component of the benzene or naphthalene series, which is formed by chlorine atoms and / or lower alkyl groups, methoxy or nitro groups or groups of the formulas -SO _n N (R) _o or -CON (R) _n , woriη R a V.'asserεtof atora and / or an alkyl group with 1 to 4 carbon atoms, can be substituted, B is the residue of an azo component of the naphthalene, pyrazolone or acetoacctarylanid series, which is represented by chlorine atoms and / or methyl, methoxy, nitro or SuIfon-. can be substituted amide groups, C the remainder of a diazo component of the benzene series, which can be substituted by the group -SO ₂ Z and / or chlorine or bromine atoms and / or methyl, thoxy or nitro groups, D the remainder of an Äzokoiaponente of the naphthalene , Pyrazolone or acetoacetarylamide series, which by the group -SO ₀ Z and / or chlorine atoms and / or methyl, methoxy, acetylamino, nitro groups or the group of the formula -SOpN (R) -, v / orin R a · ■ represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, can be substituted, X and X * for -0-, -COO-, Y and Y 'for -O-, -ITH-, Z for the group - CH = CH, (2) or - CH ₂ - CH ₂ - OSO ₃ H (3) and η stand for the number 1, characterized in that one l: l-chromium complex azo dyes of the general formula (4) 109 850/1432 A-N = N-B j anion J (4) wherein Λ, B, X and Y have the meanings given above, and [AnionJ for a non-kojaplex-forming anion with complex-forming monoazo dyes of the general formula (5) , H H, X 'Y' C-N = N-D (5) where C, D, Z, X ¹ , Y * and η have the meanings given above, in water or mixtures of water with water-miscible organic solvents at pH values between about 4.5 and 7.0 at temperatures between about 30 and 120 ° C in the presence of acid-binding agents. 11) The method according to claim 10, characterized in that the complex-forming dyes monoazo dyes of the general Formula (5a) C-N = N-D SO ₂ -CH ₂ -CH ₂ -OH (5 a) uses, and the 1: 2-chron complex azo dyes obtained of the general formula (1) mentioned dovt with the meaning -CH ₀ -CH ₀ -OH for Z by esterification nit conc. Sulfuric acid or with anidosulfonic acid in P3 ^? Ridin is converted into the 1: 2 chromium complex dyes of the general formula (1) mentioned there with the meaning -CH ₉ -CH ₀ -O-SO ₀ H for Z. 10985 0 / U 3 2 BATH O 0A unsymmeln-ΐε 12) Use of the asymmetrical mentioned in claims 1 to 9 1: 2 chromium complex dyes for coloring nitrogen-containing pens natural or synthetic fiber materials. 13) The unbalanced with the frenarmten in claims 1 to 9 1: 2-chromium corrugated loxic carbon, dyed or printed, containing nitrogen natural or synthetic fiber material. 1 0 9: i B 0 /