DE2259939A1 - AZO DYES POORLY SOLUBLE IN WATER, AND THEIR PRODUCTION AND USE - Google Patents

Description

CIBA-GEiGY AG. CH-4002 Basel WuU = J ^ If "- \ * ^ 3 '

Germany

Lawyer File 23. 131 7 Dec * 197-2

ι Azo dyes that are sparingly soluble in water, and their Manufacture and use

j The present invention relates to new, in water I.
J-

; sparingly soluble, usable as disperse dyes j azo dyes, process for their production, the

i Turn of the new azo dyes for dyeing hydrophobic ones

i · ■ -.

organic fiber material, especially textile fibers made from linear polyesters of aromatic polycarboxylic acids polyhydric alcohols or from cellulose esters and, as

j industrial product made with the new dyes

colored fiber material. . . ·

Requirement for the successful dyeing of

bath

303824/1097

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Polyester fibers are well known - along with satisfactory ones Fastness to application and use - excellent drawability of the disperse dyes used for this purpose. The dyeing of textured fiber material places particularly high demands on the dyes to be used! Polyester, e.g. Crimplenev-4 for this apart from good fastness properties and sufficient drawability, a very good build-up and leveling capacity of the dyes is essential.

Valuable azo dyes which are sparingly soluble in water have now been found which meet these and other requirements suffice. The new azo dyes do not have any acidic dissociating water-solubilizing groups in water and correspond of formula I,

-N = N-

^γΑ ? ^ (D

CHCH- OZ R ₁ R ₂

in which A is a residue of a diazo component of the aromatic or heterocyclic series, Y is a hydrogen atom or an organic residue, Z is an organic residue and R and R _? one R is hydrogen and the other is an organic radical

309824/1097 BADOR ₁ G ₁ NAL

CIBA-GEIGY AG

V- '

means.

Dyes of particular value are those compounds of the formula (I) in which Y is a lower alkyl radical, such as, for example, a methyl group or an optionally substituted phenyl radical, Z is hydrogen or an acyl radical and R and R _{2 are} optionally substituted mean lower alkyl, cycloalkyl, aryl or aralkyl radical.

ι '· ι

Preferably, D puts one through if necessary

Halogen atoms, hydroxyl, cyano, rhodan, nitro, lower

Alkyl, trifluoromethyl, lower alkoxy, formyl, lower alkylcarbonyl, benzoyl, methylbenzoyl. lower alkoxy, carbonyl, Benzyloxycarbonyl, cyclohexyloxycarbonyl, Phenoxycarbonyl, lower alkoxycarbonyloxy, benzyloxy, carbonyloxy, lower alkylcarbonyloxy, benzoyloxy, lower alkylcarbonylamino, benzoylamino, lower alkylsulfonyl, Chlorethylsulfonyl, hydroxyethylsulfonyl, unsubstituted or by lower alkyl groups, mono- or disubstituted aminosulfonyl, di (hydroxyethyl) aminosulfonyl, phenylaminosulfonyl, (Chloro- or methoxy) phenylaminosulfonyl-, Benzylaminosulfonyl-, N-piperidylsulfonyl, N-morpholino- " sulfonyl, lower alkylsulfonyloxy, cyclohexylsulfonyloxy, Chlormethylsulfbnyloxy-, Cyanäthylsulfonyloxy-,

'- -BAD ORiGiNAL

309824 / -1 097 "·"

Phenylsulfonyloxy-, aminosulfonyloxy-, (chloro- or methoxy) phenylsulfonyloxy-, N-morpholinosulfonyloxy-, Aethyleneiminosulfonyloxy, lower monoalkyl or dialkylaminosulfonyloxy, phenylaminosulfonyloxy, N- ' Phenyl-N (lower-alkyl) aminosulfonyloxy-, N- (methoxy- or chlorine) phenylaminosulfonyloxy-, phenylamino-,

Nitrophenylamino, dinitrophenylamino, phenyl, phenoxy

; and / or acetylaminophenyl groups substituted phenyl radical, . an optionally by chlorine or bromatoine, hydroxyl, Cyano, nitro, lower alkyl, trifluoromethyl, lower Alkoxy or phenoxy groups substituted phenylazo

! I.

j phenyl radical, one optionally replaced by methoxy, 'Ethoxy, phenylazo or dimethylaminosulfonyl groups . substituted naphthyl radical, one optionally by Chlorine or bromine atoms, nitro, cyano, rhodan, lower Alkyl, lower alkoxy, lower alkyl mercapto, phenyl, benzyl, phenethyl, cyano, lower alkyl, lower Alkyloxycarbonyl, trifluoromethyl, lower alkylcarbonyl and lower alkylsulfonyl groups substituted thiazolyl, one optionally by chlorine or bromine atoms, cyano-rhodan, Nitro, lower alkyl, lower alkoxy, benzyl, phenylethyl, lower alkylsulfonyl, phenyl, lower Alkyl mercapto, lower alkoxycarbonyl, lower alkylcarbonyl, Trifluoromethyl, cyanoethylsulfonyl, aminosulfonyl

309824 / .1097 BADOr ₁ GINAL

CiBA-GEtGYAG _

or a benzothiazolyl radical optionally substituted by lower mono- or dialkylaminosulfonyl groups, an optionally by cyano, lower alkyl, lower alkoxy, lower alkoxycarbonyl or phenyl ' groups-substituted pyrazolyl radical, one optionally by lower alkylsulfonyl, lower alkoxy, lower Thiadiazolyl radical substituted by alkyl, phenyl, lower alkylsulfonyl or lower alkyl mercapto groups imidazolyl radical optionally substituted by nitro or lower alkyl groups, one optionally substituted by Nitro, lower alkyl, lower alkylsulfonyl, lower alkoxycarbonyl or acetyl groups [ Thienyl radical, an isfthiazolyl radical optionally substituted by lower alkyl, cyano or phenyl groups,

- 'and one if necessary by lower ones. Alkyl groups, nitro groups or halogen atoms substituted benziso-; ' thiazolyl radical. Lower alkyl groups are, for example, methyl, ethyl, propyl, isopropyl and isobutyl radicals. ; Particularly important are the dyes in which D is a phenyl or azobenzene radical which is substituted by halogen, cyano, nitro, lower alkylsulfonyl, carboxylic acid ester, N, N _: disubstituted carbamoyl and / or sulfamoyl groups, or an optionally substituted and / or benzofused heterocyclic radical

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aromatic character means.

As acidic dissociating, water-solubilizing groups in the new dyes are excluded, the known, the dyes are anionic in character here and below conferring substituents, e.g. sulfonic acids, carboxylic acid or phosphoric acid groups, understood. ■

, The substituents listed for the phenyl radical A. can be present simply or in any combination of two or, in special cases, three.

If one of R. and FU is a lower alkyl radical, this particularly has 1 to 4 carbon atoms on. If this alkyl radical is substituted, for example lower alkoxy groups, such as Methoxy or ethoxy group, cycloalkoxy groups, such as the Cyclohexyloxy group, phenalkoxy groups, such as the benzyloxy

igruppe, aryloxy groups, especially the phenoxy group, : Acyloxy groups, especially lower alkanoyloxy groups, such as

j the acetyloxy group, the cyano group or halogens such as chlorine ^! or bromine in question.

: Cycloalkyl groups representing R. and R. For example, cycloalkyl groups are preferred

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5- or 6-membered rings and especially the cyclohexyl group into consideration.

Does one of R .. and R _mean? an aryl radical, this preferably belongs to the "benzene series; it can have customary nonionic ring substituents. Such substituents, especially on the phenyl radical, are, for example, halogens such as fluorine, chlorine or bromine, lower alkyl or lower alkoxy groups.

If one of R and R "represents a carboxylic acid

ester group, it is preferably a lower alkoxycarbonyl group, such as the carbomethoxy, Carbethoxy, carboisopropoxy or carbobutoxy group.

In the meaning of an acyl radical, Z is particularly a lower alkanoyl group, which with Voteil has -2 to 4 carbon atoms. -,

; The term "lower" before the term "alkyl", "alkoxy" or "alkanoyl" means that the group or the organic group component has a maximum of 5 carbon atoms. ·.

The new azo dyes of the formula I are obtained by adding the diazonium compound of an amine of the formula II,

A-NH ₂ (II) ■

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in which A has the meaning given under formula I, with a coupling component of formula III,

(in) ,

CH-CH-HDZ

Ii ■■■■■.

; ^R i ^R 2

in which X, Y, Z, R, and Rp are those given under formula I. Have meaning, coupled to an azo compound of the formula I.

ι The starting materials of the formulas II and III are chosen so that the azo dye obtained from in : Water acidic dissociating, water-solubilizing Groups is free.

Preferred azo dyes according to the invention are coupling products of the formula I, which under ■ Use of diazonium compounds of amines of the formula

III are produced, in the A one in p ^ position to

Azo group denotes a phenyl radical having a nitro group,

which is optionally further substituted by a cyano group, a lower alkylsulfonyl group, chlorine or bromine is. Of these coupling products are azo dyes of the formula I in which A is one in the p-position

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to the azo group means a phenyl radical which has a nitro group and which is in an ο position to the azo group is a cyano group or is further substituted by chlorine, particularly preferred.

The negatively substituted aminobenzenes represent a valuable selection of diazo components, such as e.g. those of the formula

: wherein a is a hydrogen or halogen atom, a lower one ■ alkyl or lower alkoxy, nitro, cyano, lower, alkylsulfonyl group, 'b a hydrogen or halogen atom, a lower alkyl, cyano or trifluoromethyl group, c

i *

^: a nitro, cyano, carbalkoxy or alkylsulfonyl group! and d is a hydrogen or halogen atom, a lower alkyl,

j mean alkoxy, carbalkoxy, cyano or carboxylamide group.

: Negatively substituted anilines "are those which ^: contain negative substituents, ie substituents that enhance the acidic properties of phenol or see a positive sigma value according to Hammet's

para

Own equation (Jaffe, Chemical Reviews, - Volume 53 *

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191-233, particularly Table 7; Staab, introduction to the theoretical organic chemistry, 2nd edition, 1960, Weinheim / Germany, p.

Examples include: 2-aminothiazole,.

2-amino-5-nitrothiazole,.

! 2-amino-5-niethylsulfonyl-thiazole,

'. 2-Amino-5 ~ cyanthiazole ..
2-AmInO - ^ - methyl-5-nitrothiazole, 2-amino-4-methylthiazole,

2-AmInO - ^ - phenylthiazole,

t · ■ · ■■■■ · ■ · ■ .. '

'2-Amino-4- ( ^J l' -chlor) .- pher.ylthiazol,. · ·. 2-Amino-'r- (4 '-nitro) -phenylthiazole,' 3-aminopyridine,. *. ,

3-aminoquinoline,

'3-aminopyrazole, "..

; 3-amino-1-phenylpyrazole, '. ■. ' j3-aminoindazole, '

. 3-amino-l _J 2,4'-triazole, '. .

5- (methyl-, ethyl-, phenyl- or benzyl) -1,2,4-triazole, 3-AmInO-I - (^ r'-methoxyphenyl) -pyrazole, 2-arr.inobenzothiazole,

2-amino-6-. ^r T ¹ .ethylbnzthiazole _J. .

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2-amino-6-reethoxybenzthiazole,
'2-Amino-6-chlorobenzthiazole, - ^ "2-Amino-6-cyano-benzothiazole,' ■. ^Τ - · '-.

2-Amino-6 ~ rhoäanbenzthiazol, '". ■' ■.:

2-Amino ~ 6-nitrobenzthiazol., · · '''·' -. ■■■, '■■■ \ i2-AiüIno-6-carboethoxybenzthiazole _i . . ^: _Ν "

2-amino (4- or 6) -methylsulfonylbenzthiazole,

'2-AmInO- ¹ I - phenyl- or -4-methyl-1,3 ^ 5-thiadiazoles

; 2-Arιino-3-nitΓo-5-R ■ iethylsulfo'nyl-thioph "en, 2-amino ~ 3j5 ~ bis (methylsulfonyl) ~ -thiophene,. _; 5-Araino-3-methyl-isothiazole · ■

• 2-Ämino- k -cyano-pyrazole,. . ·.

2- (4'-nitrophenyl) ^ - amino - ^ -

^r 3 ~ or ^ -aminophthalimidj
; Aminobenzenes''"'.,

! .l-Araino - ^ - broir.benzol, ■ ■. ^: . '-. '.-

.l-Amino-4-methylbenzenes' .... · _ ·.

il-Amino - ^ - nitrobenzenes · - ■ '·.' '. "- ■ ...

1 -amino -h -cya-nbenzene, '·

l-Amino ^ S-dicyanobenzene, 'BAD 0B01NAV

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l-Amino - ^ - methylsulfonylberizoli

l-amino - ^ - carbcilkoxybenzene, -;

1-Amino-2, h -dichlorobenzene, 3 -f-.r.tl i'Ki-7 '., Η -υ! bror.ilj'.n '/.'/ J, l-Amino ^ -inethyl-Ji-ehlorbenzol,; r-Amino-2-trifluororr.ethyl -k -chlorobenzene, l-Amino-2-cyano- ⁱ T- chlorobenzene, -11-amino-2-carbomethoxy-4-chlorobenzene, l-Arnino ^ -carbcrr.ethoxy - ^ - nitrobenzoli;

I l-amino ~ 2-chloro- ⁱ r-cyanobenzene., "'.

l-Amino ^ -chlor- ^ r-nitrobenzene, '. ■ ..' · '■'

. ι .- · ■■

: ^{L-amino-2-bromo-i} i-nitrobenzene, "" ■

1-amino-2-chloro -4 -carbathoxybenzene, l-amino-2-chloro- ⁱ T-methylsulfonylbenzene,

1-amino ^ -methylsulfonyl-'f-chlorobenzene, "

1-amino -2, h -dinitro -6 -rr.e thylsulfonylbenzene ,; 1-amino -2, h -dinitro-6- (2 ¹ -hydroxyethylsulfonyl) -benzene,, l-amino-2, ⁱ l-dinitro -6- (2 ^l -chloroethylsulfonyl) -benzene, i l-amino-2-ir; cthylsulfor) yl-'i-nitrobenzene _J 'ι 1-amino-2-methylsulfinyl -h -nitrobenzene,

! l-amino ~ 2, ⁱ } -dinitrobenzene, ^%

lA; nino-2,4-dicyanobenzene, 1-amino-2-cyano-h -methylsulfonylbenzol,

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l-Amino-2, h -dicyan-6-chlorobenzene, "'·.;.'

4 ~ Arriinobenzoic acid cyclohexyl ester,;. -

and particularly

l-Aniino-2-cyan - ^ - nitrobenzolj ·.

. 1-aminobenzenes, -3- or -4-sulfonic acid, v: ie the N-methyl or Ν, Ν-diethyl or diethyl amide, ·; N, 7 "Isopropyloxyprop3 ^r l-2-Srnino-naphthalene-6-sulf or.säurearnic , N, 7-IsOPrOPyIoXyPrOPyX-I-GrXiInObCnZoI-S- ^ ~ 3 ~ or - ^ - sulfcnj acid amide, -." · -. "'.".-;''':. ■ ...- ■ -

Isopropyl-1-aniinobenzene ^ -, -J> - or. -4-sulfonic acid arrtia.

NjY-Kethoxypropyl-l-aminobenzoie-, '' -3- or -h -sulfonic acid-: amide, "^ - ** -. '

■ N, N ~ bis- (ß-hydroxyethyl) -l-aminobenzenes-, -J> ~ or. -4-suircr; -: "säurearnid, '*". "■ .'-.

l-Amino - ^ - chlorobenzene-S-sulfonic acid anide, 'and the N-substituted derivatives, -

2 ~, 3 ** or ^ -Arninophenylsulfarr.at,. ·

, '2-Amino ->! -, -5- or ^ -O'-ynethylphenylsuli'arnate, . ' 2-Amino ~ 5 - '"" ethoxyphenylsulfamate, -.' . ·

: 3 ~ Amino-6-chlorophenyl sulfarnate, '· .- ■. ·

3 ~ ^Am ino-2,6-dichlorophenyl sulfate, "■ '. ·.

ty-amino-2- or -3-niethoxyphenylsulpharnate, N, N-dimethyl-2-aniinophenylsilfarnate,

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N, N-Di-n-butyl -2-ar.iinbphenylsulfarnat,

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N, K-dimethyl -2-arnIno-'i -chlorophenylsulfamate , N, n-propyl-2-a ~ .inopheriylsulfarr.at, M, K-di-n-butyl-3-ar-iinophenylsulfamate / 0 (3 -AiT: inophenyl) -N-tiorpholin ~ v ^T -sulfor.at,

0 (3-Arriinopher; yl) -X-piperidine-sulfonate,; K-Cyclohexyl -0- (3-af »« ixiopheriyl) sulfamate ,

K (W-methylaniline) -0- (3-asTiinophenyl) -sulfonat, SN, N-diethyl-3-ämino-ö-Kiethylphenyl-sulfamat, K-Aethylenimin-O- ( k -aminophenyl) - sulfonate N ^ N-Dimethyl - ^ - aninophenylsulfaniat, /

• O (n-propyl) -0- (3-ainophenyl) sulfonate,. ■

0, β-chloroethyl-0- (2-aminophenyl) sulfonate, "· 0-Benzyl-0- (3-arainophenyl) sulfonate and -

O-ethyl-0 - (^ - amino-2j6-dimethyl-phenyl) sulfate. 4-aminoazobenzenes., Which are used as a diazo component ^

can be used are ζ.3. ^ -Aminoazobenzene,

^ -Amino ^ -nitroazoebenzene, *!

, 3j 2'-dimethyl -K -aminoazoberizole,. * · ■. "

j 2-methyl-5-methoxy - ^ - a.T.inoazobenzene, - ·

4'-methoxy - ^ - aniinoazobenzene, 2-methyl - ^ '- inethoxy - ^ - aKiinoazobenzol, 3j6, h' -trimethoxy- ^ r-aminoazobenzene, V -chloro - ^ - aminoazobonzolj, 2 '- or 3' -chlorine ^ -amino.v'obenzene;

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CIiIA-GEIGYAG _ 15 -

5-nitro-4-amino-2 '_, 4'-dichloroazcbonzol and ■ ■ /'

^ -Aminoazobenzene-V-sulfonic acid amide, and generally p-azobenzene radicals; which by halogen atoms, nitro, cyano , IFLRfIx Wd / or

Nitro groups can be substituted, in particular, optionally substituted o-nitro-p-azobenzene'ste.-. ■ ' Instead of the above-mentioned, ionogenic, vrasser-

soluble, T. acnenden groups, free diazo components can also such used vrerden, v; elcho fiber-reactive groups

included, such as s-triazinyl, which bear on Triazir.i-Ir.s 1 or 2 chlorine or Broraatome, Pyrinudylreste one or two chlorine atoms or one or zv / ei arylsulfonyl or Alkansulfonj ^r lgruppen on Pj ^ rimidinring wear, mono-

; or bis (7-halo-ß-hydroxypropyl) -amino groups, ß-Halc ^ enäthylsulfamylreste, β-Hai ogenäthoxy groups, ß ^ Halogc-; ethyl mercapto groups, 2-ChI or-benzthiazolyl-6-azogr -.ppeiij 2- Chlorobenzothiazolyl-6-amino groups, ", '- halogen-β-h: - :' ~ roxy propylsulfamyl radicals, chloroacetylamino groups, α, β-dibro.T, -propionyl groups, vinylsulfonyl groups or ₅ 2;, 3-epoxy propyl groups . ·. ·. '

. -. Suitable fiber-reactive diazo components are, for example, K, β-chloroethyl-3-chloro- ^2- r-aruino-benzenesulfamide (hydro.

'Chloride.), * ■

N, 'β-chloroethyl -H -arr.inobenzol-sulf amide (Kydrochlorid)

: 3 "SrOHi- ^ i-amino - ω-chloroacetophenone, ■ ·" "·; ·

ii, 7-Chlor7ß-hydroxypropyl- ⁱ l -aminobenzene-sulfamidy _t N, β-chloroethyl-1-amino-4-naphthylsulfonamide,. ''·

N, ß-chloroethyl-1-amino-3j5- "dichlorobenzenesulfamide and '■ ij .- ('y-chloro-β-hydroxy-propoxy) -aniline. '·.,'

BAD ORIGINAL 3 Q 9 8 2 4/1 O 9 7

CIDA-GEIGYAG - Ιβ -

Those made with such diazo components. Compounds contain instead of just the inventive device present fiber-reactive acylaraino group Ac a further fiber-reactive group whose reactivity is greater or can be smaller than that of the group Ac.

j ■ ·· -The listing of the courageous Di.i.-okor.por.cnter. can in Mineral acid with sodium nitrate or e.g. with a solution of

i Kitrosylschv.-efelsriure in concentrated sulfuric acid, successful. j. . ■

The coupling can also be known per se

j V / eise, e.g. in a neutral to acidic medium, if necessary in Presence of sodium acetate or the like, the coupling speed influencing buffer substances or catalysts, such as 3. Dimethylformamide, pyridine, respectively. desr: en Salting, can be made. '.

The coupling components of the formula. I'll be able to look at it in itself

known methods produced v.-erdep., > :. 3. by the accumulation of

Epoxy compounds of the mold]. IV,

R - CH - CH ₀ (IV)

V ²

in which R is an optionally substituted lower alkyl, cycloalkyl, aryl radical or a carboxylic acid ester group corresponding to _{the radicals R or R 0, on amines of the formula V}

(V)

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The addition takes place in the presence of alkali, preferably alkali hydroxides such as potassium or Sodium hydroxide, in inert organic solvents, e.g. weakly ionizing solvents such as methyl ethyl ketone. Or preferably strongly ionizing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrzölidon, Dimethyl sulfoxide and suIfolane (tetramethylene sulfone). That Epoxide is preferably used in an excess of at least 1.2 moles per mole of indole, in particular 1.5 moles per mole of indole, used. The accumulation takes place at an elevated temperature, e.g. 30 to 200 ° C, preferably 4C to 80 ° C.

In this addition, two isomeric compounds of the formulas VIa and VIb

CH-CH ₂ OH

R- (Via) (VIb) "

arise, which are subsequently given by the general formula VI,

BAD 309824/1097

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(VI)

in which X, Y, R, and R "have the meaning given above, to be symbolized. These isomer mixtures usually contain a significantly larger proportion of the compound the formula VIa.

If Z in the formula III represents an acyl radical, the addition products of the formula VI with a acylated the compound introducing the acyl radical Z.

If you use e.g.

Dimethylformamide in the presence of small amounts of alkali

man /;

hydroxyd, .zB potassium hydroxide, then receives / the compound of the type of formula VTa in so
pure state that further cleaning is unnecessary.

Examples of epoxies are:

^! 1,2-epoxybutane, 2,3-epoxybutane, the glycidyl esters of acrylic, methacrylic, benzoic, palmitic or stearic acid, glycidyl tosylate, glycidylcarbanilate (glycidyloxycarbonylaminobenzene) and epoxyethylbenzene (styrene oxide), furthermore glycidyl ether compounds, such as ethyl ether compounds her, glycidyl- ■ isopropylätiier, 1-glycidyl-2-methoxyethane, 1-glycidyl-2-ethoxyethane,

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- lo ft -

Methyl glycldyl ether

Methyl-a-methylglycid-yl ether

Methyl-ß-methylglycidyl ether

Ethyl-ß-methylglycidyl ether

n-propyl glycidyl ether

n-propyl-ß-methylglycidyl ether

i-propyl-ß-methylglycidyl ether

n-butyl glycidyl ether

η-Butyl-β-methylglycidyl ether

i-butyl glycidyl ether

i-Butyl-ß-methylglycidyl ether

tert-butyl glycidyl ether

tert-butyl-ß-methylglycidylethyl

n-amyl glycidyl ether

n-amyl-ß-methylglycidyl ether

n-hexyl glycidyl ether

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-l8b-

CIBA-GEIGYAQ

n-Hexyl-ß-methylglycidyl ether

n-Heptyl glycidyl ether B.

n-heptyl-ß-methylglycidyl ether

Benzyl glycidyl ethers

Benzyl-ß-methyl-glycidyl ether

Allyl glycidyl ether

Allyl-ß-methylglycidyl ether

Methyl glycidyl ether

Methyllyl-ß-methylglycidyl ether

Phenyl-ß-methylglycidyl ether

o-tolyl glycidyl ether

1-tolyl glycidyl ether

Phenyl glycidyl ether

Pentachlorophenyl glycidyl ether

α-naphthyl glycidyl ether

α-naphthyl-ß-methyl glycidyl ether

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ß-Naphthyl glycidyl ether

β-naphthyl -β -iraethylglycidyl ether

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1-Glycidy1-2-butoxyethane, l-glycidyl-2-phenoxyethane, * 1-glycidyl-2-benzyloxyethane, 1-glycidyl-2-methoxyethoxyethane, 1-glycidyl-2-ethoxyethoxyethane,

1-glycidyl-2-butoxyethoxyethane, -

1-Glyc i d y 1 -2-phenoxyethoxyethane, l-glycidyl-2-benzylaxyethoxyethane, l-glycidyl-2-butoxyätboxyäthoxyäthan, l-Glycidyl-2-phenoxyethoxyethoxyethane of the formula

C 0

and 1,2-epoxy-3-phenoxypropane and 1,2-epoxy-3- (p-nitrophenoxy) propane.

Examples of coupling components which can be used according to the invention are:

t. " ■ · .. ■■,

1_ (2'-hydroxypentyl) -2-methylindole; 1- (2 ^I -hydroxybutyl) -2-methylindole 1- (2'-hydroxypropyl) -2-methylindole 1- (2'-hydroxyacthyl) -2-methylindole 1- (2'-hydroxypentyl) -2-phenylindole

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l- (2'-Hydroxybutyl) -2-phenylindole -

l- (2'-hydroxypropyl) -2-phenylindole l- (2'-Hydroxyacthyl) -2-phenylindole · l- (l ^l -Hydroxyrnethylbutyl) -2-methylindole.

1- (l ^f -hydroxymethylpropyl) -2-methylindole l- (l'-hydroxymethyl) -2-methylindole l- (l'-hydroxymethylbutyl) -2-phenylindole

1- (1'-hydroxymethylpropyl) -2-phenylindole . l- (l'-hydroxymethylacthyl) -2-phenylindole ·; 1- (2'-Hydroxy-3'-phenoxypropyl) -2-methylindole

1- (2'-hydroxy-3'-methoxypropyl) -2-methylindole ■ 1- (2'-hydroxy-3'-phenoxypropyl) -2-phenylindole

1- (2'-Hydroxy-3'-methoxypropyl) -2-phenylindole • ^{1- (2!} -Acetoxybutyl) -2-methylindole -1- (2'-acetoxypropyl) -2-methylindole

i- (2 ^f -acetoxybutyl) -2-phenylindole ^: 1- (2'-acetoxypropyl) -2-phenylindole, 1- (2'-acetoxy-3'-phenoxypropyl) -2-methylindole. 1- (2 ^L -acetoxy-3 ¹ -methoxypropyl) -2-methylindole · 1- (2 ^f -acetoxy-3'-phenoxypropyl) -2-phenylindole.

1- (2 ^! -Acetoxy-3 ^f -methoxypropyl) -2-phenylindole

According to the invention, sparingly soluble in water can be used Azo dyes of the formula I, ■ in the Z one Acyl radical, also produce by one

30982 A / 1097

Azo dye of the formula VII,

CH-CH-OH ( ^νΐΙ λ- »

I I

in which D, Y, R and Rp have the meaning given above, with a compound introducing the acyl radical Z, the starting materials being chosen so that the final dye of the formula I does not have any water-solubilizing groups which dissociate acidically in water.

Azo compounds of the formula VII are obtained

for example by coupling the diazonium compound of an amine of the formula II with a coupling component of formula VI, the coupling being carried out as described above.

Suitable compounds for introducing the acyl radical Z are, for example, the acylating agents mentioned below.

The reaction of the azo compounds of the formula VII with the compounds introducing the acyl radical Z. takes place in a suitable organic solvent]., such as in glacial acetic acid or dioxane, optionally in the presence of one

BATH ORIGINAL 30982W 1 097

CIBA-GEIGYAG

acid binding agents such as sodium acetate., magnesium oxide or pyridine. "'.

The following acylating agents can be used to introduce the acyl radical into the azo dye of the formula (VII) or into the coupling ^{component: of the formula IHa:}

^: Aliphatic ^ acid chlorides, such as acetyl chloride, propionyl

chloride, α-bromosepylsene chloride or bromide, n-butyryl ^; Chloride, grotonic acid chloride, 2-methyl mercaptopropionyl chloride, 4-chlorobutyryl chloride, araliphatic carboxylic acid halides such as phenylacetyl chloride or p-nitrophenylacetyl chloride, cycloaliphatic acid chlorides such as cyclobutanecarboxylic acid chloride, 5-norbornene-2-; carboxylic acid chloride, aromatic carboxylic acid chlorides, such as 'benzoyl chloride, o-, m- and p-methyl and' ethylbenzoyl chloride * I o-, m- and p-methoxy and ethoxybenzoyl chloride, 1- or naphthalenecarboxylic acid chloride, 3j ^ -di ⁿ itrobenzoyl chloride,

: 2,4- or 3j ^ -olchlorobenzoyl chloride , p-phenylazobenzoyl-:

j ■ ■■ - '.

■ chlorides of 2-anthraquinonecarboxylic _{acid chloride, heterocyclic;}

> Carboxylic acid halides, such as furan-2-carboxylic acid chloride, 2-thenoyl chloride, 2-thienylacetyl chloride and nicotinic acid chloride and carboxylic anhydrides, such as acetic anhydride, n-butyric anhydride, iso-butyric anhydride, cyclo-

BAD ORIGINAL 30982A / 10 97

CLBA-GEIGY AG

SiL

butanecarboxylic anhydride, benzoic anhydride, p-chlorobenzoic anhydride, 2-furanic anhydride and Nicotinic anhydride.

Mixed anhydrides can also be used, such as the anhydrides made from acetic acid and Benzoic acid or β-naphthoic acid, whereby in the legel

■ Mixtures of dyes are created.

■ If necessary, you can also use the free

Run out of acids when the acid halide or the Anhydride are difficult to access.

! ¹ p.

Sulfonic acid halides suitable as starting materials for the actual reaction are benzenesulfur: acidic. Chloride, o- and p-ToluenesulfonsäurecliloriajS ^ l-, 2,5- or>,; ^: Dimethyl-ber.zolsulfonsäurechlorldj 3, ^, 5- or 2, 'ί, o-Triir.ethy; benzenesulfonic acid chloride, tetralin-Y-sulfonic acid chloride, p- ■ nitrober, benzenesulfonic acid chloride, 2-kethyl-5-chlorobenzene-sulfonic acid chloride, 5 - ^ 'ethyl-thiophene-2-sulfonic acid chloride and metha: sulfochloride.

Instead of the chlorides, it is also possible, if appropriate, to use fluorides, bromides or iodides of the acids.

BATH ORIGINAL

309824/1097

CIBA-GEiGYAG

Examples of reactive carbonic acid derivatives are in question: '

ClCOSC ₂ H ₅ ClCOOC ₂ H 'ClCONHC ₂ H ".

CICOSCH ₂ CH ₂ Ci 'CICOOCh ₂ CH ₂ CI. CICONKCH ₂ Ch ₂ CI-

• CICOSCKpCK'OCK · ClCOOCH CH OCH. CICONHCHpCH OCH,

d c- 2 d d *) d d J

cicoscK ₀ CH ₀ ocK cicooch ₀ ch ₀ oocciL · ciconkch ₀ ch ₀ oocck-.

c- d d d Jt d 2 p

ClCOSCAh. ClCOOCH, - -ClCOXKCK

'' ■ ο!) ■ 05, 05

ClCOSC ₆ H ₄ OCH ₃ ClCOOC ₆ H ₄ OCH ^ ClCONKC ₆ H _r OCH

UXOvJov ^ rli.AU, -, OlUUüO ^ -iiι, Λυ_ ν / ΙΟυλπν / ru. ΐ ·· υ_

O ^l td O ¹ I d O 'i 2

V / urther Acylierungsirattel are the alkyl and aryl isoc5 · ^r anate and heterocyclic isocyanates, v / ie eg K Aethyüsocyaiiat ethylisocyanate, n-Propylisocyanate r.-3 - .; tylisocyar.5T. _; Octyl isocyanate, Kethyl isocyanatoacetate, Butyi isocyanatoacctate. Cyclohexy! Isocyanate Phenyl isocyanate p-tolyl isocyanate, o-, m- and p-chlorophenyl isocyanate, m- and p-nitrophenyl isocyanate, 2e5-dichlorophenyl isocyanate, o- and p-methoxy isocyanate 2-kaphthy 1 isocyanate 2-} 3-phenyl isocyanate 2-isocyanatotetrahydropyran, tetrahydropyran, tetrahydropyran, Isocyanatopyridine, 2-furyliso-. cyanate ^ -Isocyanato-N-ethylearbazole and preferably isocyanates schvrefelhaltiger heterocycle ^ Viie 2-Carborfiethoxy-] 5-isoc5'anatcthiophene 2-Isocy a na to -J> - cyano-thiophene 2-Isocyanato-3-carbomethoxy-4-rr; ethyl-thiophe "ne 2-isocyariato-5-ίr.ethyl-thiophene-2-carboxylic acid arriide 2-isocyanato-3-carboirietho" * "" ^ -dimethyl-th; cp) :.

309824/1097 BAD OR.G.NAL

C; iüA-GiitGY AQ

2 ~ Isocyar.ato-3-carboethoxy-j5 _J 'ί-te trarr.e thy len-thiophan and. jj-isocyanato-sulfolane; and isothiocyanates of the formula

ZN = C = S,. .how
Ethyl isothiocyanate, n-dutyiisothiocyanate and phenyl isothiocyanate

The new azo dyes of the formula I represent yellow, orange, red to brown crystalline substances that are sparingly soluble in water. By recrystallization from organic substances Solvents they can be obtained analytically pure, but such a purification is for their use for Coloring is generally not necessary.

The new dyes, their mixtures with each other

I ■ ■

and their mixtures with other azo dyes, are excellent for dyeing and printing leather, full, Silk and especially synthetic fibers, v.'ie for example Acrylic or acrylonitrile fibers made from polyacrylonitrile or from mixed polymers, from acrylonitrile and others

Vinyl compounds, such as acrylic esters, Acrylair.i & en, vinyl pyridine, vinyl chloride or vinylidene chloride or from copolymers of dicyanoethylene and vinyl acetate, as well as from acrylonitrile block copolymers, fibers from polyurethane, polypropylene fibers such as cellulose tri- and 2 l / 2-acetate and especially fibers made of polyamides, such as} \ ^T yl ° n ~ 6, nylon-6,6 or nylon 12 and from aromatic polyesters, such as those made from terephthalic acid and ethylene glycol] or 1, '-! - Di me thy 1--

30982 ^ / 1097. BATH ORIGINAL

CIBA-GEIGV AG -

as »

cyclohexane and copolymers of terephthalic and isophthalic acid and ethylene glycol «.. ·· -_ '·.

· For dyeing in aqueous liquors one uses the water-insoluble dyes in finely divided form and dyes with the addition of dispersants, such as Sulphite cellulose waste liquor or synthetic detergents, or a combination of different wetting and dispersing medium .. As a rule, it is zv.-eekrnäGsig. 'those to be perished. To convert dyes into a dye preparation before dyeing., which is a dispersant and finely divided dye in such a form that when the dye preparations are diluted with water, a fine dispersion is formed. Such dye preparations can be used in a known manner,

e.g. ¹ . can be obtained by grinding the dye in dry or wet form with or without the addition of dispersants during the grinding process. · ~. ·

To achieve strong dyeings on polyethylene terephthalic fibers If it proves expedient to add a swelling agent to the dyebath, or the dyeing process to be carried out under pressure at temperatures above 100.degree. C., for example at 120.degree. Suitable swelling agents are aromatic carboxylic acids, for example salicylic acid, Phenols, such as, for example, o- or p-oxydiphenyl, aromatic Halogen compounds such as o-dichlorobenzene or diphenyl. To thermoset the dye "is

BATH 30982Λ / 1097

CIBA-GEIGYAG

Sb

padded polyester fabric, appropriate after previous Drying, e.g. in a warm air stream, to temperatures from above. 100 ° C, for example between 180 to -210 C, heated The obtained according to the present process

Colors know a · X'ach'cohar.dlurig subject v / ground, for example by heating with an aqueous solution .an ion-free detergent ^.

Instead of impregnating, according to the pre-

a process also carried out the specified dyes Imprint can be applied. For this purpose, one uses, for example, a printing ink that is next to that in the printing house common aids, such as wetting agents and thickeners, contains the finely dispersed dye.

The present process gives strong dyeings and prints with good fastness properties. ^: The new water-insoluble dyes can also be used for spin dyeing of polyamides, polyesters and polyolefins. The polymer to be colored "is intended

in bulk in the form of powders, grains or chips, as a finished spinning solution or in the molten state mixed with the dye, which in the dry state or in

In the form of a dispersion or solution in-one, if appropriate volatile solvent is introduced. After homogeneous distribution of the dye in the solution or melt of the Polymers, the mixture is made in a known manner by casting

0 9 8 2 4/1097 ^BAD

CIBA-GEIGY AG

sen, pre-press or extrude into fiber, yarn, Kono threads, films, etc. processed. -

In the following examples, the mean

Unless otherwise indicated, parts are parts by weight , percentages are percentages by weight, and temperatures are in

Degrees Celsius. - ^: -. · '"·

BAD 30982A / 1 097

CIBA-GEIGYAG -

XZ

example 1

17 * 3 S l-amino-2-chloro-4-nitrobenzene are diluted in Hydrochloric acid is diazotized with an amount of aqueous sodium nitrite solution corresponding to 6.9 g of sodium nitrite.

; The diazonium solution obtained is at Q-5 C to an emulsion of 20.3 S 1 ~ (2-hydroxybutyl) -2-methylindole in 250 ml of water and 25 ml of Tinegal Na added dropwise. Man stir the coupling solution for 16 hours and then filter the precipitated dye of the formula

CH ₂ -CH-CH ₂ -CH ₃

OH -

away. It is washed neutral with water and dried at 60 to 70 ° C. in a vacuum. -

'' This mixture turns - after grinding with the sodium salt of a condensation product of naphthalene-2-sulfonic acid with formaldehyde - from an aqueous dispersion in the presence of sodium-o-phenylphcnolat as a swelling agent Polyäthylenglykolterephtalatfasern in brilliant orange very light well, washing, reib - and sublime tones. <The one used in this example] as the coupling component

3 0 9 8 2 4/1097 BAD ORIGINAL

ag

l - (2-Hydroxybutyl) -2-methylindole is obtained by adding 2 methylindole together with 1,2 butylene oxide in dimethylformamide heated to 60 to 80 ° C with the addition of catalytic amounts of potassium hydroxide.

Example 2

13.8 g of 1-amino-4-nitrobenzene are dissolved in dilute hydrochloric acid diazotized with an amount of aqueous sodium nitrite solution corresponding to 6.9 S sodium nitrite. i) ie received Diazonium solution is added at 0 to 5 ° C. to an emulsion of 20.3 g of 1- (2-hydroxybutyl) -2-methylindole in 250 ml of water and 25 ml of Tinegal Na were added dropwise. The coupling solution is stirred for 16 hours and then filtered precipitated dye of the formula

- CH ₂ -CH-CH ₂ -CH ₃ OH

away. It is washed with water and stored at 50 to 60 ° im Vacuum dried. -

This dye dyes polymethylene glycol terephthalate ice from a fine aqueous dispersion, e.g.

309 8 2.4 / 1 09.7

CIBA-GEIGY AG

Crimplene ^ in pure golden yellow tones.

The coupling component / is produced as described in example 1.

■ Example 3 - ^r '

17 * 3 ß l-amino-2-chloro-4-nitrobenzene v / earth in dilute Hydrochloric acid is diazotized with an amount of aqueous sodium nitrite solution corresponding to 6.9 g of sodium nitrite. The received Diazonium solution is added dropwise at 0 to 5 G to a solution of 28.1 g of 1- (2-hydroxy-3-phenoxypropyl) -2-methylindole in 300 ml of glacial acetic acid and 50 ml of water, whereupon the dye of the formula

Cl

-N = N-

CH ^Ν

CH ₂ -CH-CH ₂ -OH

ruled out. It is filtered off, washed with water and dried at 60 to 70 ° C. in vacuo. After the marriage with ligriine sulfonate, this dye from an aqueous dispersion stains poly ethyl englyko 1 terephthalate fibers very much

30982471097

8p ORIGINAL

CIBA-GEIGYAG

pure orange tones. The colorations are well light- and sublime. , ".-. '.». ■..'

The 1- (2-hydroxy-3-phenoxypropyl) -2-methylindole used in the example as a coupling component is "obtained by adding 2-methylindole together with 1-phenoxypropylene oxide-2, 3 in dimethylformamide with the addition of potassium hydroxide to 60% heated to 80 ^° C. ■

' Example 4 . ■ -

17.3 1-Amino-2-chloro-4-nitrobenzene are diazotized in the usual way in dilute hydrochloric acid. On the other hand, 24.5 g of 1- (2-ethoxy-butyl) -2-methylindole are emulsified in 250 ml of water and 25 ml of Tinegal_Na. These "tr _o pft one at 0 to 5 ° C, the diazonium slowly, the dye of the formula ~ '■ what ■

CH ₂ -CH-CH ₂ -CH ₃ OCOCH ^

ruled out. It is filtered off, washed with water and

309 8 2 47 1097

BATH

shows a melting point of 16 ^J l C.

Those with this dye on polyethylene glycol terephthalate fibers yellowish orange dyeings produced are characterized by good lightfastness, good Wet fastness and good rub fastness.

The 1- (2-acetoxybutyl) -2-methylindole used as coupling component in this example is obtained from Acetylation of 1- (2-hydroxybutyl) -2-methylndoil, its Preparation is described in Example 1, with acetyl chloride in pyridine at 25 to 35 ° C

Example 5

17.3 l-Amino-2-chloro-4-nitrobenzene are used in usual Way diazotized in dilute hydrochloric acid. The resulting diazonium solution is at 0 to 5 C to a solution of 20.3 g l- (2-hydroxybutyl) -2-methylindole and l- (l-IIydroxymethylpropyl) -2-methylindole in 600 ml 80% acetic acid added dropwise, whereupon the dye mixture of the components of the formulas

BATH ORIGINAL 30 98 24/1097

CLBA-GEIGY AG

.OH ₂ -CH-CH ₂ -CH ₃ OH

Cl.

HO-CH ₀ -CH-OH ₀ -CH ^

ruled out. It is filtered off, washed neutral with V / ater and dried at 60 to 70 C in a vacuum. This Mixture dyes polyethylene glycol phthalate fiber from an aqueous dispersion in pure orange tones. The dyeings obtained are very good rub, light and

sublime right. -

The mixture used in this example as a coupling component of approx. 65% l ~ (2 ~ hydroxybutyl) -2-methylindole and 35 $ 1- (I-hydroxymethylpropyl) -2-methylindole is obtained by adding 2-methylindole together with 1, 2-Butylene oxide in dimethyl sulfoxide with the addition of catalytic amounts of potassium hydroxide is heated to 80 to 90 ° C. In the above examples 1 to 4, the

30982A / 10 9 7

BATH

Diazo component by the corresponding amount of one of those indicated in column II of the table below Diazokoraponenten and coupled them under "the conditions described in the above examples corresponding amounts of one of the coupling components indicated in column III, one obtains dyes, - the Polyethylene glycol terephthalate fibers give dyeings of similar good properties and their shades in the in the last column of the table.

BATH ORIGINAL

309824/1097

Example no.

II

Diazo component

ei ■■

O ₂ N-

N _x

NCS ^ Cl Cl ^ I C-NH ₀
A _3/2 Ν _χ Y. C-NH
Ag / 2

Tabel

III

CH.

CH.

CH.

CIL

CH,

CH-

CH.

CH

CH ₂ -CH-y - OZ

30 9 8

CH ₂ -CH ₃

CH ₂ -CH ₃

₀ -QK ₇ 2 3

CH ₂ -CH

CH ₂ -CIL,

CH ₂ -CH ₃

247 1,097

Huanee on PoIyaethylenylykolt ej phthalate fibers

reddish orange

yellow-brown

yellow

reddish yellow

golden yellow

yellow

red-brown

red-brown

II

HO

III

COOCJiL

y * -

O ₀ N-ClV-NH ₀

ά d.

OJM? V-NH,

18 19 20 21 22

24

do.

OIL

CH.

CH.

OIL

CH ₂ -CH ₅

CH ₂ -CH

CH ₂ -CH ₅

CH ₂ -CH ₅

CH ₂ -CH ₂ -CH- H

CH ₂ -CH

. fifj rru

do ■ _{"_:} CH

30S824 / 1097

IV

Red

yellow-brown

Scarlet fever ■

yellowish orange

yellowish orange

reddish yellow

reddish yellow

COCHJ orange

COCHb orange

H yellow

II

yellow

II

26th

27

28

29

do.

do.

Cl > 2 ^N -CIMH ₂

do. do.

31

do.

do.

33

34

do.

do.

do.

do.

CH.

CIL

CH.

CIL

CIL

CIL

Ill

CH.

CI

CH,

CH ₂ -CH ₃

CH.

CH ₀ -CH ₀ -CIL! H dd ρ

COCIL

COCIL

COCH.

COCH.

QOCH,

0.9 8-24 / 109 7

CII

IV

yellow

reddish yellow

reddish yellow

orange

orange

reddish orange

reddish orange

orange

orange

orange

reddish ο rare. ge

reddish ο now BAD ORIGINAL

'• A

II Cl
•
> -NH ₂ do. N-C3 CN do. . do. do. do. do. do. do. do. do.

III

CH.

CiL

CIL

3098

CH ₂ -CH ₅

CH ₂ -CH ₂ -CH H

CH ₂ -CH ₅

CH.

COCH.

! H ₂ -CH ₂ -CH

3IL

II

CH ₃

IUI 1097

II

COCIL.

reddish orange

reddish orange

reddish orange

reddish orange

reddish orange

reddish orange

yellowish scarlet fever

yellowish scarlet fever

yellowish scarlet fever

yellowish scarlet

ιό ts tichig ο ran ße

... ' CÜCiL. ¹ fcharlach
"^; i ' ^J \ - BAD ORIGINAL

C C O ί "

II

ν = /

50 i do.

do,

56

57

58

do.

Cl

do. "

CIT

dor.

Cl

60 ■

CH.

CH.

CH.

CH.

ch;

OIL

'CH.

CH

III

CH ₂ -CH;

■ Ή.

5

CH ₂ -O-CH

, ^: Η

CH ₂ -O-CH H

CH ₂ -O-CH ₃ ο

CH _o ~ () - <3

.24 / 1.0 07

.. I.

. H

IY

orange

orange

orange

yellow

reddish yellow

golden yellow

orange

orange.

orange

reddish orange

reddish orange

yellow

BAD ORfGINAL

II

CN

(CH, -)

Cl

Cl

III

χ! y

CIL

CH

CIL

Cl

CH ₂ -CH

CH ₂ -CH,

CH ₂ -CH ₅

IV

yellow orange yellow yellow

BATH ORIGINAL

309824/1017

CIBA-GEIGY AG

«■ / Γ - 4? -

Examples (Table 2)

I. II; ■ 0
If X OH, O O O JII do Z 5 H IV 65 Il r ~ \
H ₂ N. C (V-NH ₂ do CH ₅ y do H 66 Cl ^) - NH ₂ do
I. do OHj do do COCH COCH ₇ orange 67 do HOCHaO ^ wUrQ-NH ₂ do do do OCH ₂ Cl . 2 ^ 5 orange 68 do do do do do ', H orange 69- do. do do do do Ή. COCH ₇ orange 70 do
p do rusty
yellow 71 do ZIl ₇ OCH ₀ CH ₀ C- C V-NH ₀
J dd -. ■ d do X) CH ₂ CH-, reddish
yellow do do do reddish
yellow 72 do 3o H 75 do yellow ■ v \ do yellow 75 do yellow 76 do yellow . 77 do yellow 78 ' do yellow 79 yellow yellow roll; ■

30 9 8-2 4/10 97

BATH

CIBA-GEIGY AG

81

82 85

84

86

87 88

89

90 91 92

93

II

do do

NO ₂ QNNQ-NH ,,

do do

Cl

CH

do

on

NC — NH ₀

do do

N (C

do do

NH

NH ₀ do

III

CH

do

do
do

do
do

do
do

do

CH ₇

H ₀ .CH

do do

do

do do

do do ''

do

do do

do

do do

do

flo

309824/109 7

H'

OCH ₂ Cl '

OCH

OCH ₀ CH,
5

COCH ₀ CH

COH

COCH-

|.-1K ¹ M ₀ CH.,

yellow

yellow yellow

orange

orange orange

reddish yellow

reddish yellow

orange

orange

orange

orange

or a ge

orange

vi olott

. iolOtt

BATH ORIGINAL

Beispi el q j

1 part of the dye obtained in Example 1 is mixed with 2 parts of a 50 $ - <Lgen aqueous solution of the Wet grinding of the sodium salt of dinaphthylmethanedisulphonic acid and dried.

This dye preparation is stirred with 40 parts of a 10% aqueous solution of the sodium salt of N-benzyl · μ-heptadeeyr-benzimidazole disulfonic acid and Ψ parts of a 40% acetic acid solution are added. By diluting it with water, a dye bath of 4000 parts is prepared,

In this bath you go at 50 with 100 parts one cleaned polyester fiber, increases the temperature

turner to 120 to 130 within half an hour and colors _; one hour in a closed vessel at this temperature. Then it is rinsed well. A brilliant orange dyeing of excellent lightfastness and sublimation fastness is obtained.

309824/1097

Example 9'S '"

20 parts of the dye obtained in Example 2 are l ^; 40 parts of water, welohe.s 40 parts of sodium dinaphthylmethanedisulphonic acid, grind.

A padding liquor is prepared from 200 parts of the above dye preparation, 100 parts of carboxymethyl cellulose ( ¹ I $ aqueous solution) and 700 parts of water by stirring the dye preparation described above into the prediluted thickening using a high-speed stirrer and then adding 80% to the mixture. £ acetic acid adjusts to a pH value of 6. In this liquor, a fabric made of polyester fibers is padded with 50 % and a squeeze effect of 60% and then dried at 70 - 80. The fabric is then heated to 210 on the stenter for 60 seconds and then washed hot and rinsed well with cold water. A fabric is obtained which is colored golden yellow with good fastness properties.

BATH ORIGINAL

309824/1097

- irtr-

Example 99
Printing on polyester fabric

25 parts of the finely ground dye of the formula are mixed
Cl

CH ₂ -CH-CH ₂ CH
Oh

550 parts of 8 ^ -ige 'aqueous thickening from modified locust bean gum ,

550 parts of a 10 ^ solution of the sodium salt

. of m-nitrobenzenesulfonic acid,

10 parts of a mixture of potassium oleate and pine-011

and make up to 1000 parts with water.

With the help of a high speed stirrer, the mixture is
Stirred until the dye is completely dispersed and then printed on polyethylene terephthalate with this paste

Steamed minutes at 1 1/2 atmospheres, rinsed with cold water for 10 minutes, twice hot with the addition of a little
Soaped with hydrosulfite, rinsed with cold water and dried. Man
acquires a true orange color.

BATH ORIGINAL

0 9 8 2 4/1097

Example 100. Dyeing of polyester fibers in an organic solution medium

10 g of textured polyethylene glycol terephthalate knitted fabrics in a liquor ratio of 1:10 at room temperature placed in a dye bath, which was obtained by 2 g of a dye preparation consisting of from 0.1 g of the dye according to Example 16, 0.04 g of Antaron V 216 (polyvinylpyrrolidone with a molar weight of approx. 7000) and 1.86 g of paraffin oil dispersed in 98 ml of tetrachlorethylene will.

The dyebath is heated to 121 while the material to be dyed is constantly agitated and at the boiling point for 50 minutes of tetrachlorethylene held.

After cooling, it is rinsed at 80 with tetrachlorethylene containing 0.25 % Ilexamethylphosphorsäuretriamid, rinsed again with 80 warm tetrachlorethylene and then dried.

A brightly colored, flat, flat, scarlet-red color is obtained Coloring with excellent light, sublimation, Wet and rub fastnesses.

BATH ORIGINAL

309824/1097

Claims (1)

CiBA-GHIGY AG S4 Claims 1. Slightly soluble in water, free from acidic dissociating, water-solubilizing groups Azo dyes of the formula I, CH-CH-Ο? II ' R ₁ K ₂ in the Λ a residue of a diazo component of the aromatic \ or heterocyclic series, Ύ a hydrogen atom or a ■: hydrogen or / ■ '. 'organic residue, Z j ' an organic ~ ITesc and from R _n ^- and R; a.R is hydrogen and the other is an organic radical. .- ·· .. · 2. Azo dye according to claim 1, wherein Ύ is a lower alkyl radical or an optionally substituted phenyl radical, Z is hydrogen or an acyl radical and R ₁ and Rp are an optionally substituted lower alkyl, cycloalkyl, aryl " or aralkyl radical. ·. · . BATH 309824/1097 CIBA-GtIGYAQ _ 3. Azo dyes according to claim 2, wherein Y is a methyl radical or an optionally substituted one Phenyl radical is, Z is a hydrogen atom or an acyl radical 4. Azo dyes according to Claims 1 to 3 * .due to this characterized in that A is an optionally substituted phenyl radical) an optionally substituted radical the thiazolyl, benzthiazolyä, benzthiazolyl, pyrazolyl, Thiadiazolyl, imidazolyl, thienyl, isothiazolyl or Isobenzothiazolyl radical, or a radical of the formula <Av-W = N- (B in which the rings A and B are replaced by halogen atoms, alkyl, cyano and / or Nitro groups can be substituted; is. 5 ·. Azo dyes according to claim H _1, characterized in that A is a benzene radical which has at least one substituent with a positive one Sigma value.
° para 6. Azo dyes according to Claims 1 to 5 » characterized in that they are derived from a coupling component in which Z is a hydrogen atom or is an alkylcarbonyloxy or a benzoyloxy radical. y. Process for the preparation of azo dyes of the formula (I) which are sparingly soluble in water BATH ORIGINAL 309824/1097 CIBA-GEIGYAG -. '§ · θ- ~ C3 Λ —JT = N- ^ ■ ι ι in which A is a residue of a diazo component of the aromatic or heterocyclic series., Y is a hydrogen atom or Hydrogen or / an organic radical, Z / an organic radical 'and of R and Rp one R is hydrogen and the other is an organic radical., Characterized in that the diazonium compound of an amine of the formula (II) "■' - ■ ■ A-NH ₂ ■; '· in which A has the meaning given under formula (I), with a coupling component of the formula (ill) Y ^Χ CH-CH-OZ
^R l in the R., R _? , Y and 7, which have the meanings given under I, are coupled to form an ^ azo compound of the formula (I). BAD ORIGINAL 309-8 24/1097 CLBA-GEIGY AG 8. Modification of the process according to claim 7 for the preparation of sparingly water-soluble azo dyes of the formula I, in which Z represents an acyl radical , characterized in that an azo dye of the formula VII, A -N = N- CH -CH-OH in which A, Y, R and Rp have the meaning given in claim 7 , with a compound introducing the acyl radical Z. 9. A method for dyeing or printing hydrophobic organic fiber material, characterized by the use of azo dyes of claim 1. 10. The method according to claim 9 * characterized in that fiber material based on synthetic linear polyesters or cellulose acetate is used. BATH ORIGINAL 309824/1097 CIBA-GEIGYAG 11. Dyestuff preparations, characterized in that they are sparingly soluble in water, free of acidic dissociating, water-soluble-making groups in water of the formula I, ' _a ". _; " - A-N = Y N CH-CH-OZ '' Il R ₁ R ₂ in which A is a radical of a diazo component of the aromatic or _y heterocyclic series, Y is a hydrogen atom or a Hydrogen or / organic radical, Z / an organic radical and. one of R- and Rp is hydrogen and the other is an organic radical. ""< 12. Amines of the formula wherein Y is a lower alkyl radical or an optionally is substituted phenyl radical, Z is hydrogen or an acyl radical and R-, and R ^ one R is optionally substituted lower alkyl / cycloalkyl, aryl or Ar alky Ire st means. ■■■■ "- ·., BATH ORIGINAL, 309 8 2 Λ / 1 097