DE1816985A1 - Basic azo dyes and process for their preparation - Google Patents

Description

FARBfERKE HOECHST AG. formerly » U * Im fr Lueius ft Brünlnf file number: p * 5966

2o. December 1968 Dr> Cz / Kö

Basic azo dyes and processes / -zii their manufacture

The present invention relates to basic azo dyes, which are free of sulfonic acid groups and the general Formula (I) / "_;

CS ¹ -

* ■

H -

(I)

where E _{1 is} an optionally substituted alkyl radical j R is hydrogen, an optionally substituted alkyl _S ; Aralkyl or Iryl radical, R, an optionally substituted alkyl or aralkyl radical _? B an aromatic or heterocyclic Eest _? Z denotes a hydroxyl group, a primary secondary or tertiary amino group and X® denotes an anion and the benzene radical denotes a further © nonionic®. Sulistitueiiteii-can contain _o

009829/1319

BATH ORIGINAL

2 -

The dyes can be obtained in such a way that a) the diazonium compound of a quaternary amine of the general Formula (II)

NH ₂ H ₁

(II)

wherein R ,, Rp, R ^, & and Jr have the meaning given above, with azo components of the formula (III)

B - Z

(III)

in which B and Z have the meaning given above, or that b) an azo dye of the general form Ji (IV)

N · N - B - Z - R-,

(IV)

where R ,, R ~, yes, B and Z have the meaning given above own, treated with alkylating agents.

The quaternary amines used for procedure a) of the formula II can by treating amines of the formula (V)

MH ₂ H ₁

(V)

wherein R,, R ^ and el have the meaning given above, with quaternizing agents _v such as alkyl halides, aralkyl halides, haloacfetamides, β-H & logenpropionitriles, halohydrins,

009829/1319

BATHROOM OBlGlNAL

Alkylene oxides, acrylic acid amide, alkyl esters of sulfuric acid or organic sulfonic acids.

Suitable amines of the formula V are 4 (7) -aminotrifluoromethylbenzimidazoles, which in addition to the trifluoromethyl _{group may contain other nonionic substituents in the benzene radical, for example halogen atoms, alkyl, 9} alkoxy, trifluoromethyl, nitro, aryloxy, acylamino or cyano groups.

Die'Biazotlerung the amines for Forsel II takes place according to methods known per se, for example by means of hydrochloric acid and sodium nitrite _{or the like}

The coupling with the azo components of the formula III is in a manner known per se, for example in a neutral or acidic medium, optionally in the presence of buffer substances or agents which accelerate the coupling, such as Pyridine.

According to the process, the azo components of the formula III are used in o- or p-position to a hydroxyl group or a aromatic or heterocyclic compounds coupling primary, secondary or tertiary amino groups, which are free from sulfonic acid groups. From the series on this suitable azo components which couple in the o- or p-position to a hydroxyl group are aromatic or heterocyclic Mention should be made of hydroxy compounds and those compounds which have an enolizable or enolized ketomethylene group contained in a heterocyclic ring. Such connections are for example Phenol, the 4-substituted derivatives of the Phenols, such as p-cresol, p-chlorophenol, ^ -hydroxy-l ^ -xylene, 4-hydroxyacetophenone and hydroquinone monomethyl ether, the derivatives of α-naphthol substituted in the 4-position, such as 4-chloro-1-naphthol, 4-methoxy-1-naphtol and 4-benzoyl-inaphtol, ß-naphtol and its derivatives, such as 6-bromo-2-naphtol, 7-hydroxy-2-methoxynaphthalene, l-benzoylamino-7-naphtol and ^ -Benzolazo-l-amino ^ y-naphtol, and 6-hydroxyquinoline,

'009829/13 19 - * -

8-hydroxyquinoline, 3-hydroxydiphenylamine, 2-hydroxycarbazole, 3-hydroxydiphenylene oxide and l-aryl-3-methyl-5-pyrazolone. In addition to these * monohydroxy compounds come as Azo components also in o-position to the hydroxyl groups coupling polyhydroxy compounds of the aromatic or heterocyclic series into consideration, for example resorcinol, Benzoylresorcinol, terephthaloylbisresorcinol, 2,6-dihydroxynaphthalene, 2,4-dihydroxyquinoline and 3,6-dihydroxydiphenylene oxide. Alkyl or aryl amides of aromatic or heterocyclic o-hydroxycarboxylic acids are also suitable or of acyl acetic acids, for example alkyl or aryl amides of 2,3-hydroxynaphthoic acids, 2-hydroxycarbazole-3-carboxylic acids, 3-hydroxydiphenylene oxide-2-carboxylic acid, the Acetoacetic acid or benzoylacetic acid.

Of the azo components which can be used according to the process and which are in the o- or p-position to a primary, secondary or Coupling tertiary amino groups, aromatic or heterocyclic amino compounds should be mentioned. As primary amines For example, aniline, toluidines, xylidines, anisidines, phenylenediamines, tolylenediamines, aminocresol ethers, Alkoxyanilines, chloranilines, 3-acylaminoanilines, Dialkoxyanilines, naphthylamines and heterocyclic amines, such as, for example, 5-aminopyrazoles, 7-aminoindazoles or 8-aminoquinoliney under consideration. As secondary or tertiary For this purpose, amines are suitable compounds in which the radical B belongs to the benzene or naphthalene series, and furthermore as further substituents, for example halogen atoms, alkyl, alkoxy, carbalkoxy, carboxy, alkylsulfonyl, carbamyl, SuIfamyl, amino, trifluoromethyl, acyl or acylamino groups may contain. For the secondary or tertiary amino group Z are, for example, lower substituents Alkyl radicals, such as methyl, ethyl, propyl or butyl radicals, or aralkyl, cycloalkyl or aryl radicals of importance, in which optionally further substituents, such as halogen atoms, hydroxy, cyano, acyloxy, carbalkoxy, Carbamyl, dialkylamino, phenyl, alkoxy, acyl, dicarboximido, alkyl sulfone, aryl sulfone, alkyl sulfone 1-

00 9 829/1319 - 5 -

amino » _? , SuIfamyl- or Phenosygruppoii can be represented ,, In the tertiary amines can form hierbei'die Alkylgpuppen optionally also with itself or together with an oxygen atom or -Stickstoff- hydrogenated hetero rings such as piperidine _»t morpholine or piperazine ring.

Such compounds are also used as azo components contemplated, both a hydroxy and an amino group contain, such as aminophenols or

Le ...

The azo dyes of the formula XV used for procedure b) can be prepared in a manner known per se by coupling the diazotized amines of the formula V with azo components of the formula III or by condensation of the amines of the formula Y with the corresponding p-nitroso compounds of tertiary aromatic amines of the formula III are obtained "Suitable alkylating agents alky! halides _{t t} Jtralkylhalogenide halogenoacetamides, ß-Halogenpropionitrile, halohydrins, alkylene oxides" acrylamide, alkyl esters of sulfuric acid or alkyl esters of organic sulfonic acids, Suitable alkylating agents include methyl chloride, »bromide or" iodide, Ithyl bromide or ooäidj propyl bromide or iodide, benzyl chloride, chloropropionitrile ₉ ethylene chlorohydrin, dimethyl sulphate, diethyl sulphate, methyl benzenesulphonate, methyl p-toluenesulphanate. "Ethyl =, -propyl = or -butyl ester" The alkylation takes place regularly in an inert organic solvent, for example in a hydrocarbon _? Chlorohydrocarbon or oil hydrocarbon ₉ such as bensol _$ toluene ₉ xylene _s fetrachloroethane ,, chlorine Q-form, fetrachlorocarbon _s mono- orodoxy dichlorobensol or Mtrobansol _s in one acid aiside or acid ahydria.5 such as diaethylformaldehyde _{or acetic acid sulfide 9} ! «Hethy! A ketone, such as Icetone or EthylethyiketoiXo, instead of an organic solvent, also a Cffaersoliusis of Al ^ lating agent

* Biosan

508823/1319

will. Depending on the number of alkylatable nitrogen atoms of the starting dye become one or more alkyl groups introduced into the dye molecule. The alkylation is carried out at an elevated temperature, optionally with addition of acid-binding agents, such as magnesium carbonate »soda, calcium carbonate or sodium bicarbonate, and optionally under pressure. * The most favorable conditions in each case can easily be determined by means of a preliminary test.

The dyes obtainable according to the invention preferably contain the remainder of a strong acid, for example, as the anion χ " sulfuric acid or its half-ester, an aryl sulfonic acid or a hydrohalic acid. This according to the procedure Introduced anions can also be replaced by anions of other acids, for example phosphoric acid, Acetic acid, oxalic acid, lactic acid or tartaric acid replaced will. The dyes can also be obtained in the form of their double salts with zinc or cadmium halides.

The new dyes are suitable for dyeing or printing tannin cellulose fibers, silk, leather or fully synthetic fibers such as acetate silk, polyamide fibers or acid-modified polyester fibers, but especially fibers containing polyacrylonitrile or polyvinylidene anide. The dyeings available on these fibers are usually very clear and strongly colored and generally have good light and good wet fastness properties, for example good fastness to washing, fulling, over dyeing, carbonizing, chlorine and perspiration, as well as good decaturation, steaming "Fastness to ironing, rubbing and solvents." are also at Teisperaturen Oberh & It LX (i ^J G-- as sia at ck-p ^ Kocb cffiperaturfärberci reasonable T / ieno.Qt ■ • rs.roep, ü ^^ täfiCig "PRR" le ^ frae dpp ^ li the dyes under normal! c · "' ¥ lh ^ ji3'b ^' ^: i: -ug: u:>, pj a Vo

U Ü 3 Ö £ \ tt ί «3 ^: » «ϊ

BATH ORIGINAL

example 1

5-Trifl \ iormethyl-7-amino-a-methylbenzimldazole (RG .: 99%, mol 215) are mixed with 500 parts by volume of water and 25 parts by weight of magnesium oxide, it is heated to 60 ^° C. and then left in the course of 1-2 hours 150 parts by volume of dimethyl sulphate in the mass dropwise such that the temperature remains at about 60 ⁰ C. The mixture is stirred at 60-65 ⁰ G 2 hours, filtered off after addition of 5 parts by weight of diatomaceous earth "and 2.5 parts by weight of activated carbon and washed in 3 batches with each 110 parts by volume of hot water to" spell is one 4-0Θ parts by volume of 30% hydrochloric acid are added and cooled to 0 - 5 ⁰ C. After addition of 300 parts by weight of ice is diazotized with 205 parts by volume 511-Natriumnrbritlösung After the end of diazotisation destroyed a small Nitritübefschuss with about 2-3 parts by weight Aminosulfοsäure and then leaves the clear, yellow-brown.. Biazo solution is poured into a well-stirred mixture of 185 parts by weight of NB-Oyanäthyl-N -äthylanilin and 300 parts by volume of ice water .60 dried at 70 ⁰ C. It is approximately ² KX) parts by weight of the dye of formula is obtained

N - CH

N =

C ₂ H ₄ CN

in the form of red crystals that easily dissolve in water and dilute acetic acid with a yellow-red color.

1 g of dye is mixed with 3 g of 50% acetic acid and dissolved in 5 liters of water. The dyebath is still with 1 g of crystalline sodium acetate and 10 g of calcined

009829/1319

Glauber's salt offset ^. Then the fiber is at 60 C with 100 g of prewashed yarn Polyacrylnitrilstapel ~ in the dyebath, raising the temperature to 100 ⁰ C and stained for one hour at boiling temperature. It is then slowly ^{cooled to 60 °} C., rinsed and dried. · The result is a clear, reddish orange coloration with very good light and wet fastness properties.

Example 2

16 parts by weight of 1-ethyl-2-methyl-5-trifluoromethyl-7-aminobenzimidazole dichlorohydrate are in 300 parts by volume of water after adding 40 parts by volume of 5N hydrochloric acid diazotized at 0 - 5 ° C in the usual way with 10.5 parts by volume of 5N sodium nitrite solution. After destruction 8.5 parts by weight of 3-methyl-N, N-diethylaniline are added dropwise to a slight excess of nitrite with a little aminosulfonic acid in the course of 30 minutes. The crystalline precipitated bluish-red hydrochloride of the dye is Sucked off after uncoupling, washed with water and mixed with 500 parts by volume of water. Then it will be adjusted to a pH of about 8-9 with sodium hydroxide solution, after 3 hours the yellow-red dye of the formula

GH ₃

N ^ ^ N - CpHc

⁵ -C ₂ H ₅

-n ^ p-n;

CF, CH, ^υ 2 ^η 5

Sucked off, washed with water and squeezed well. For conversion to the quaternary compound is stirred the wet filter cake in 500 parts by volume of toluene is dehydrated by azeotropic distillation and can after addition of 0.5 parts by weight of anhydrous sodium carbonate or 0.5 parts by weight of magnesium oxide in the course of 1 hour at 80 ⁰ C 5 parts by volume of dimethyl sulfate dropwise. To ·

. '■ -: ■ .. 0 09829/1319 -9-

"When the quaternization is finished, you suck the one in dark red Crystals precipitated dye of the formula "

CH, OSO < 0 0

off, washed with toluene after until the filtrate is colorless expires and dried at 60-80 ⁰ C. Man 27 Gewiehtsteile receives a clearly soluble in water or dilute acetic acid, blue red color product "

20 g of dye are dissolved in 50 g of β, β'-dioxydiethyl sulfide, 3Q g of cyclohexanol, 50 g of JO ^ iger acetic acid and 400 g of water and stirred into 4-50 g of crystal rubber thickening 1: 2. A fabric is made with this printing ink Polyacrylonitrile staple fiber printed. The print obtained is dried, dampened atm 3p minutes at 0.5, at 50 ⁰ C with 1 g / l of a condensation product of oleic acid and soaped MethyItaurin and cured as usual. A well-fixed, red print with very good light and wet fastness properties is obtained.

The table below contains more according to the invention available dyes as well as the shades of the Dyes available on polyacrylonitrile fibers:

10

0 0 982971319

Of

R ₂ « B-Z X " 1816985 ^R l methyl ^E 3 3-methyl-N, N-di-
ethylaniline CH ₅ SO ₄ hue ethyl methyl methyl 3-methyl-N-ethyl
N-ß-cyanoethylaniline Br bluish a
Red ethyl water
material methyl N-ß-cyanoethyl-2-
naphthylamine egg bluest ichige s
Red methyl water
material methyl 3-methyl-N, N-bis-
ß-cyanoethylaniline Cl bluish tint
Red methyl water
material methyl 3-methyl-5-pyra-
zolon-1-amidine Cl orange methyl water
material methyl 3-methyl-l-phenyl * -
5-pyrazolone Cl reddish
yellow methyl water
material methyl 2-methylmerc apt o-
4-amino-6-oxy *
pyrimidine Cl yellow methyl water
material methyl 2-oxynaphthalene Cl yellow methyl Benzyl methyl 3-methyl-N, N-di-
ethylaniline Cl orange methyl water
material methyl 3-methyl-N, N-di-
ethylaniline Cl bluish tint
Red ethyl water
material ethyl 2,5-dimethoxy
aniline Cl bluish tint
Red methyl water
material methyl 1-aminonaphthalene Cl yellowish
Red methyl water
material methyl l-phenyl-5-amino-
pyrazole Cl Bordo methyl water
material methyl N-ethyl-N-ß-meth-
oxyethylaniline Cl greenish
yellow methyl water
material methyl N-ethyl-N-ß-acet-
oxyaniline CH ₅ SO ₄ Scarlet fever ethyl water
material methyl N-ethyl-K-ß-cyano-
ethylaniline CH ₃ SO ₄ Scarlet fever ethyl water
material methyl 3-methyl-H, N-bis-
ß-acetoxyethyl
aniline ZnCl ₄ Scarlet fever ethyl water
material methyl 3-methyl-N-ethyl
N-ß-oxyethylaniline 2 Scarlet fever methyl CH ₃ SO ₄ ethyl bluish tint
Red

00 98 29/1319

BATH ORIGINAL - ··

methyl

ethyl

ethyl

ethyl

methyl

methyl

methyl
methyl

methyl
methyl
methyl
methyl
methyl

methyl
methyl
methyl
methyl

Methyl. methyl

Methyl methyl,

Hydrogen, methyl

Hydrogen, methyl

Hydrogen, methyl

Methyl methyl

Methyl methyl

methyl

hydrogen

hydrogen

hydrogen

hydrogen

Hydrogen , '

hydrogen

Methyl methyl

Methyl methyl methyl methyl methyl

Wämser- methyl fabric

Hydrogen, methyl

Hydrogen, methyl

Hydrogen, methyl

B-Z

hue

^ -Methyl-N ^ N-bis-Cl ß-acetoxyethylaniline

3-chloro-N, N-di-Cl ethylaniline

3-chloro-N, N-diethylaniline

1,3 ~ dioxybenzene

N-methyl-N-ßacetoxyethylaniline

N-ethyl-N-ß-cyano-Cl äthylaniline

N-ethyl-N-ß-oxy-Cl ethylaniline

1 _T 3-dioxybenzene Cl

3-methyl-N, N-di-Cl ethylaniline

3-methyl-N-räthyl- CH _x SO ₂ , N-ß-oxyethylaniline ^y * N, N-diethylaniline

H-ethyl-N-ß-oxyethylaniline

CH ₃ SO ₄

Cl

N-ethyl-N-ß-acet-Cl oxyäthylani1in 3-Methy1-N, N-b i s-

ß-acetoxyethyl

aniline

N-methyl-N-ß-acetoxyethylaniline

3-methyl-N-ethylaniline

1,3-dioxybenzene

Cl

ilin

3-cbcy on

009829/1319

Cl

Cl

Cl

orange

geIbstigen s Red

CH ₃ SO ₄ red

CH

, SOy, reddish ⁵ * yellow

CH, S0 ₄ scarlet fever

orange

bluish tint Red

yellow

bluish tint Red

bluish red

Red

yellowish red

Scarlet fever

Scarlet fever

Scarlet fever

Golden yellow

orange

- 12 -

ORlGlNAU

water
material ^E 5 - 12 - x " Cl 1816985 ^R l water
material methyl B-Z Cl Cl hue methyl water
material methyl 2,6-dimethylaniline ZnCl ₄ Cl orange methyl water
material methyl N-ethyl-N-ß-carlD-
amyl-ethylaniline 2 Cl Scarlet fever water
material methyl 3-methyl-N-ethyl
ü-ß-dimethylamino-
ethylaniline ZnCl ^ Cl methyl Oxy
methyl methyl 3-methylaniline 2 Cl orange Methoxy
methyl; methyl 3-methyl-N, N-di-
ethylaniline methyl water
material methyl 3-methyl-N, N-di-
ethylaniline orange ß-oxy-
ethyl water
material ß-carb
amyl
ethyl 3-methyl-N, N-di-
ethylaniline Red methyl methyl '3-methyl-H, N-di-
ethylaniline Red methyl N-methyldiphenyl-
amine Red methyl Red methyl Red

009 8 29/1319

Claims (2)

- 13 patents claims Basic azo dyes that are free from sulfonic acid groups are and the general formula CF, K-B-Z - N - Rn C.
ι where R _{1 is} an optionally substituted alkyl radical, Ro is hydrogen, an optionally substituted alkyl, aralkyl or aryl radical, IU is an optionally substituted alkyl or aralkyl radical, B is an aromatic or heterocyclic radical, Z is a hydroxyl group, a primary, secondary or tertiary Amino group and Xr ^ mean an anion and the benzene radical can contain other nonionic substituents. 2) Process for the production of basic azo dyes, characterized in that one a) Diazonium compounds of quaternary amines of the general formula -H ₂ wherein R, an optionally substituted alkyl radical, Rp denotes hydrogen, an optionally substituted alkyl, aralkyl or aryl radical, R * denotes an optionally substituted alkyl or aralkyl radical and jß denotes an anion and which can contain Bensolreet and other nonionic substituents, with Asokoaponenten der Forsel 009829/1319 - 14 - * 14 - wherein B is an aromatic or heterocyclic radical and Z denotes a hydroxyl group or a primary, secondary or tertiary amino group, couples, or " b) azo dyes of the general formula where R-, an optionally substituted alkyl radical, R ₂ hydrogen, an optionally substituted alkyl, / aralkyl or aryl radical ^ B an aromatic or heterocyclic radical and Z a hydroxyl group or a primary, secondary or tertiary amino group and the benzene radical ji further nonionic May contain substituents, treated with alkylating agents, with azo dyes that are free from sulfonic acid groups and the general formula on ve i Mn, where Β-, CF, N-N-B-Z R, - N NR ₁ - ' Z and 2M have the meaning given own, be preserved. 009829/1319 SAD ORIGINAL