DE2319230A1 - NEW COLORS, THEIR PRODUCTION AND USE - Google Patents

Description

New dyes, their manufacture and their use

\ - The present invention relates to new valuable dyes of the formula. "

■ ' R.

wherein R ₁ and R_ optionally substituted alkyl groups "which are interrupted by heteroatoms, and R ₁ and Rp" .. - ■ _ can form a 5- or 6-ring together with the nitrogen atom on the aromatic nucleus, X.. an NH group or an oxygen atom and R an organic radical, but preferably an optionally substituted phenyl radical, a pyridine radical or a radical of the formula '■ ·

is, where R ^ and R have the meaning given above,

309843 / 109Ö

The new dyes are obtained by e) adding one molar equivalent each of the coumaric acid of the formula

of the hydrazine and the carboxylic acid of the formula \ HOOC - R

in any order up to the oxadiazole ring closure in • Presence of a dehydrating agent or

b) a salicylaldehyde of the formula

R ₁

i. N-

ι ν.

wherein R-, Rp and X are the same as in formula Ί . "with a nitrile of the formula. ·

, wherein R is the same as in formula I. R stands for an aliphatic, araliphatic, cycloaliphatic, aromatic or heterocyclic radical. As aliphatic Residues come e.g. lower alkyl groups, phenoxyalkyl groups, N-alkylated -CONHp groups or carbalkoxy groups are possible. The araliphatic radicals are, for example, the benzyl or the Phenethyl radical ain question. As cycloaliphatic radicals e.g. ' "the cyclopentyi- and the" cyclohexyl radical "in question.

3 0 9 8 4 3/1090

The aromatic radicals R include, for example, fluorenyl, naphthyl or preferably phenyl radicals, which are represented by halogen atoms such as chlorine, bromine, fluorine, or by lower alkyl, lower alkoxy, lower carbalkoxy, optionally lower alkylated carbonamide, nitro, cyano, trifluoromethyl, Hydroxyl and / or optionally lower alkylated amino groups can be substituted. as heterocyclic radicals come, for example, pyridine, thiophene, furan, furfuryl, thiazole, benzthiazole or tetramethyl ensulfonres te in question, which have the same substituents how the phenyl radicals can carry.

R, and Rp denote alkyl radicals which can be the same or different from one another, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl radicals, substituted alkyl radicals, such as β-chloroethyl, ß-hydroxyethyl, ß-cyanoethyl, γ-cyanopropyl, ß-methoxyethyl, ß-acetoxyethyl, ß-butyryl-hydroxyethyl, methoxycarbonylethyl, ethoxycarbonylethyl, phenylethyl or benzyl radicals. Interconnected residues R-, and R _? form, for example, the piperidine or morpholine ring.

- 3a 309843/1090

The preferred dyes correspond to the formulas

X)

wherein Y and Z each represent lower alkyl, ₃ lower alkoxy, hydroxy groups, or halogen and / or hydrogen atoms.

v. ■■ ■■ ·· ■ ^l

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The manufacturing process a), in which 2 moles of carboxylic acid are reacted with 1 mole of hydrazine is carried out in stages according to a preferred embodiment. First one of the two carboxylic acid components or both are reacted with hydrazine and then the condensation takes place.

If you first set the carboxylic acid of the formula

HOOC - R with hydrazine, the further reaction takes place as follows

. ^ IfS-OOOH +

- ¹ ^ VAoA _x

If the two carboxylic acids are identical, the ^! . i

the following special case

R.

COOH

The latter symmetrical dyes are also usually formed as by-products when the components of the ^; Formulas

309843/1090

231923d *

0OH

HN ₂ -NH-CO-C

are condensed with each other. ". ■

The symmetrical dyes can also be obtained by a stepwise reaction with hydrazine by the dihydrazide of the formula is first used in the usual manner

-N

^X IU

and then in the presence of dehydrating agents heated.

The symmetrical dyes are preferably prepared from the abovementioned components in a one-shot process.

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23192a *

If one reacts one molecule of acid with one molecule of hydrazine, the second acid molecule can be as follows deposit in the second stage

The dehydrating agents used are e.g. phosphorus oxychloride, phosphorus pentoxide, conc. Sulfuric acid, oleum and most importantly Polyphosphoric acid. j

The dehydration takes place at 60 to 200 ° C,

preferably 80 to 180 C; one uses hydrazides as Intermediate stages, the hydrazides are formed beforehand '

Acids /

in the heat of hydrazine and the / acid esters or acid

Chlorides.

The new dyes result in particular after conversion into a finely divided form, e.g. by wet or dry grinding, pasting, falling over with textile auxiliaries, and / or organic solvents in particular

valuable dye preparations with surfactants. -!

For example, surfactants of the nonionic group which can be used advantageously may be mentioned: addition products of 8 moles of ethylene oxide with 1 mole of p-tert-octylphenol, of 15 or 6 moles of ethylene oxide on castor oil, of 20 moles of ethylene oxide on alcohol C-. gH «OH, ethylene oxide addition products to di- [α-phenylethyl! phenols, polyethylene oxide tert-dodecyl thioether, polyamine-polyglyeol-

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ether or addition products of 15 or 30 mol of ethylene oxide to 1 mole of amine C "Hp NH" or C gH "NHp. ;

As anionic surfactants or dispersants,

called ': sulfuric acid esters of alcohols of the fatty series

■ ■ - •

having 8 to 20 carbon atoms, of. Ethylene oxide adducts of the corresponding fatty acid amides, or of alkylated phenols with 8 to 12 carbon atoms in the alkyl radical, sulfonic acid esters with alkyl radicals with 8 to 20 carbon atoms ^ sulfation products of unsaturated fats and oils _? Phosphoric acid esters with alkyl radicals with 8 to 20 carbon atoms and finally fatty acid soaps. ;

Suitable cationic surfactants are quaternary ammonium compounds which contain alkyl or aralkyl radicals

Contain 8 to 20 carbon atoms. |

As an organic solvent, for example, dimethyl • ^! formamide, dimethylacetamide, dimethyl sulfoxide, tetramethylene sulfone, hexamethylphosphoric triamide or tetramethylurea j are possible. The dyes can be dissolved or, preferably, in a fine dispersion.

The new dyes, their mixtures with one another and their mixtures with azo dyes are particularly suitable

draws for dyeing and printing leather, wool, silk i and especially synthetic fibers such as j Acrylic or aeryl nitrile fibers made from polyacrylonitrile or from mixed polymers, from acrylonitrile and others

309843/1090

2319239 "

• Vinyl compounds such as acrylic esters, acrylamides, Vinyl pyridine, vinyl chloride or vinylidene chloride or from

Copolymers of dicyanethylene and vinyl acetate, as well as _; made of acrylonitrile block copolymers, fibers made of polyurethane

! thanen, polypropylene fibers such as cellulose tri- and 2 l / 2-acetate

and especially polyamide filaments such as nylon-6, nylon-6,6 j
I or nylon 12 and from aromatic polyesters such as those

from terephthalic acid and ethylene glycol or 1,4-dimethy1-

; cyelohexane and copolymers of terephthalic and isophthalic acid and ethylene glycol. i

ι:

For coloring in aqueous liquors, the water-insoluble dyes are advantageously used in finely divided form

jForm and colors with the addition of dispersants such as

i!

'' Sulphite cellulose waste liquor or synthetic detergents,

• or a combination of different wetting and dispersing

I ■.

!middle. As a rule, it is advisable to use the

! Dyes before dyeing in one of the dye preparations mentioned above transferring a dispersant and fine

contains distributed dye in such a form that when Dilute the dye preparations with water a fine

j dispersion occurs. ■ j

To achieve strong colors on polyethylene terephthalate fibers it proves to be expedient to add a swelling agent to the dyebath, or to add the dyeing process under pressure at temperatures above 100 C, for example

309843/109

231923O _x

; wise to be carried out at 120 C. Suitable as swelling agents aromatic carboxylic acids, for example salicylic acid, phenols, such as, for example, o- or p-oxy diphenyl, aromatic Halogen compounds such as o-dichlorobenzene or

• diphenyl. '^;

j The fou.-ilardized Polyester fabric, useful after previous

• Drying, ζ.Bs in a warm air stream, or with overheated > temp steam of over 100 C, for example between 180 to

| 210 ° C, heated. j

The dye obtained according to the present process

"exercises can be subjected to a follow-up treatment,

'for example by heating with an aqueous solution

■ an ion-free detergent. !

Instead of impregnating, according to the present Process the specified dyes also by printing be applied. For this purpose one uses

I .- - 1

j -e.g. a printing ink that, in addition to those in the print shop:

[common aids, such as wetting agents and thickeners, '

• _ j

contains the finely dispersed dye. j

The present process gives strong dyeings and prints with good fastness properties. j You can use the new water-insoluble dyes

jauch for spin dyeing polyamides, polyesters and polyolefins use. The polymer to be colored is

- massive in the form of powders, grains or chips,

309843/1090

^! as a finished spinning solution or in the molten state with "the dye mixed., which in the dry state or i in the form of a dispersion or solution in an optionally

; volatile solvent is introduced. After more homogeneous ι

; Distribution of the dye in the solution or melt of the : Polymers, the mixture is in a known manner by casting

[sen, compression or extrusion into fibers, yarns, monoj;

! threads, films, etc. are processed. \

j.

j In the following examples, the parts

j Unless otherwise stated, parts of the mass that

Percentages by weight, and the temperatures are in ι ■

j degrees Celsius indicated,
i

3-0 98 A3 / 1090

example 1

One carries a mixture consisting of 20.9 Share the compound of formula

COOH

(obtained by saponification of the corresponding alkyl ester with dilute Sodium hydroxide solution at 100 °) and 2.72 parts of hydrazine chlorohydrate, at a temperature of 130 in 200 parts Polyphosphoric acid, whereupon the mixture obtained is mixed at 130 to 135 for 1 hour. One lets Add 15 ml v / ater and pour on the mixture 1.1. Liters of water at room temperature, the dye formed separating out as a fine filling. One heats up the mixture to 50 ° and mix in for 50 minutes

j this temperature what one. the dye filtered off. ! ·. ^:

j The suction filter is slurried again in 200 ml of water at j 40 °, the pH value is corrected to j ₃ with soda, heated briefly to j 60 and the filling of the dye at 50 is suctioned off. It is washed with water at 50 ° and the dye is then dried in vacuo at 70.

The dye of the formula is obtained

309843/1090

as a yellow powder, which dissolves in organic solvents with a yellow color. The solutions show in daylight an intense yellow-green fluorescence. '

■ As a fine dispersion from an aqueous bath on polyester when applied, brilliant green-tinged

■ yellow colorations with excellent sublimation fastness.

If you use the same procedure otherwise, instead of the initially listed diethylamino-coumarin carboxylic acid, equivalent amounts of the corresponding N-diyne ethylamino- or N-dipropylamine-coumarin-carboxylic acid, see above dyes with similar properties are obtained.

Example 2

A mixture consisting of 10.45 parts of 7- (N-diethylamino) -coumarin-5-carboxylic acid and 5 * ^ 5 parts of benzhydrazide is added to 120 parts of polyphosphoric acid at a temperature of IJO Mixes for hours at I50 - 135 °. 5 ml of water are now added and the mixture is poured into 500 ml of kO water. The resulting dye filling is stirred in cold for some time, then filtered, washed neutral with water and dried in vacuo at JO. ;

The product obtained is a mixture of the color

. ' substances of the formulas "s

309843/1090

• Ν — Ν

and

, which is applied as a fine dispersion of aqueous bath

; adorned, brilliant greenish-yellow colorations on polyester fabric with good fastness properties. '

A separation of the dye mixture into its two components is possible, for example by chromatography on a silica gel column from a solution in the mixture of toluene-acetone 4: 1 ..;

If you use anis parts with otherwise the same procedure of benzhydrazide equivalent amounts of pyridine-4-carboxylic acid hydrazide, the dye of the formula is obtained

without the addition of the symmetrical biscumaryl dye.

309843/10 90

231923Ga *

When applied from an aqueous dispersion to polyester fabric, brilliant greenish-yellow dyeings with good results are obtained Authenticity properties. . ;

Instead of benzhydrazide in the above example, equivalent amounts of those in the table below are used listed hydrazides, dyes with similar properties are obtained. These represent mixtures of the in the Table listed dye and the symmetrical biscumaryl dye of the above example. The dye mixtures obtained were by column chromatography in as is known, separated into their components. ■.,

- 14a -

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Tabel

N-N

H ₂ IJ-HITOC

H ₂ N-HNOC

H ₂ N-HNOC H ₂ N-HNOC

H ₂ N-HNOC

H ₉ N-HNOC ι

CH

Cl

Cl

H ₉ N-HNOC

'H ₉

₉ N-HNOC

H ₃ CCT

H ₂ N-HNOC H ₉ N-HNOC -O

si

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231923 (f * ~

Hydrazide

H ₂ Ii-HNOC-CON

H ₂ N-HNOC-CH H ₂ N-HNOC-C ₂ H H ₂ N-HNOC-C ₃ H H ₂ N-HNOC-C ₄ H ₉ H ₂ N-HNOC

/ CH

r ■>

H ₀ N-HNOC-COOC ₀ H,

-CON
\

/ CH,

CH,

-CH.

-C ₂ H ₅

-C

-COOCJL

Example 3

Mix a mixture consisting of 3 * 9 parts of 2-0xy-4- (N-diethylamino) * - benzaldehyde, 4.1 Share the connection

! the formula

(obtained by ring closure of cyanoacetylbenzoylhydrazide with phosphorus oxychloride), 0.4 part of glacial acetic acid, 0.2 part Piperidine and 20 parts of ethanol for 2 hours at a temperature of 80 °. The mixture is then cooled and

309843/1090

: isolates the precipitated dye by filtration.

The obtained dye of the formula
"- NN

. can by recrystallization from, for example, ethyl

cellosolve can be obtained pure. It is identical with the \ corresponding dye of Example 2 and shows the same 'dyeing properties.
; Dyeing instructions: - -

ι ————————————

'1 part of the color obtained according to Example 1

: substance is wet ground with 2 parts of a 50 % aqueous solution of the sodium salt of dinaphthylmethanedisulfonic acid and dried.

This dye preparation is stirred with 40 parts of a 10 $ aqueous solution of the sodium salt of N-benzyl-μ-heptadecyl-benzimidazole disulfonic acid and 4 parts of a 40 % acetic acid solution are added. A dye bath of 4000 parts is prepared from it by diluting it with water. ■■. . ■

100 parts of a cleaned polyester fiber material enter this bath at 50 °, raise the temperature to 120 to 130 within half an hour and dye it in a closed vessel at this temperature for one hour. Then it is rinsed well. A strong yellow dyeing of excellent lightfastness and sublimation fastness is obtained,

309843/1090

Claims (1)

231923Ö 1. Dyes of the formula Patent applications where R and R "optionally substituted alkyl groups, which can be interrupted by heteroatoms, and R-, jind Rp 'can be located together with the nitrogen atom on the aromatic nucleus, / borrowed nitrogen atom form a 5- or 6-membered ring / ~ X is an NH group or an oxygen atom and R is an organic radical. ! 2. Dyestuff according to claim 1, characterized. .that R is an aliphatic aromatic, araliphatic i. ; is cycloaliphatic or heterocyclic radical. "ι 5, dyestuff according to claim 2, characterized by the formula i 3 0 9 8 4 3/109 0 ! ^R 2 ^R 2 wherein X, R and R_ are the same as in claim 1. 4. Dyestuff according to claim 2, characterized by the formula wherein Y and Z each represent lower alkyl, lower alkoxy, Nitro, cyano, carbalkoxy, carbonamide, trifluoromethyl, Hydroxyl groups, or halogen and / or hydrogen atoms stand. 5. Dyestuff according to claim 2, characterized by the formula "■ '' · ■ Ή - Ή ; ρ H ir. V C-R '-! ¹ O- iworin R 'is a heterocyclic radical, in particular a radical is of the pyridine, thiophene or furan series. ^; 6. Dyestuffs according to one of the preceding claims 1 to 5 j characterized in that they are free of acidic, water-soluble groups. ■ 7. "Process for the preparation of dyes of the formula 309843/1090 NH
1 \ Y _R / xr ¹ y where R, and R "optionally substituted alkyl groups, which can be interrupted by heteroatoms., and R and Rp together with that located on the aromatic nucleus Nitrogen atom can form a 5- or 6-ring, ft E X is an NH group or an oxygen atom, and R is an or- is/
ganic remainder / characterized in that one either a) one molar equivalent of the coumaric acid of the formula GOOH ; of the hydrazine and the carboxylic acid of the formula I HOOC - R ■ in any order up to the oxadiazole ring closure: ' converts / I in the presence of a dehydrating agent / or b) a salicylaldehyde of the formula ■ wherein R ₁ , Rp and X are the same as in formula I. 3098 4 3/10 9 231923Θ and a nitrile of the formula wherein R is the same as in formula I. ; 8. The method according to claim J _t, characterized in that the intermediate of the formula ^R l \ (ήΛ — COOH wherein R, > Rp and X are the same as in claim 1 with the hydrazide of the formula H ₂ N - NH - R. . I. in which R is the same as in claim 1. 9. The method according to claim 7, characterized in that 2 molecules of the carboxylic acid of the formula COOH • Reacts with a hydrazine molecule. j ι ■ ■; 10. The method according to claim 9, characterized in that the acid hydrazide of the formula is used as the intermediate product used. 309843/1090 11. The method according to claim Y _3, characterized in that the intermediate of the formula ; "2. ^R 2 dehydrated. 12. The method according to claim 9 _f, characterized in that the acid R - COOH is the compound of the formula Ni-COOH used. 15. The method according to claims 7 to 12, characterized i ^; indicates that the dehydrating agent used is phosphorus iPhoroxychloride, Pho sphor pent oxy d, Schvief elic acid, oleum, and i { \ Polyphosphoric acid used. j ; 'ι ΐ Method according to claim IJ) _3, characterized in that ! ■ - 'i that polyphosphoric acid is used. \ ■ 15. Dye preparations, characterized in that I j .they have at least one sparingly soluble in water, from in Water acidic dissociating, water-solubilizing groups' .free dye of the formula I, I. K / 3 0 9 8 43/10 9 0 in which R, and Rp are optionally substituted alkyl groups, • which may be interrupted by heteroatoms, and R ₁ and Rp · together with that located on the aromatic nucleus Nitrogen atom can form a 5- or 6-membered ring X an NH group or an oxygen atom and R an or-, is,/
ganic reserve. .16. Dye preparations according to claim 15 ₃ characterized indicates that they contain a dispersant. VJ. ' Dyestuff preparations according to claims 15 and 16,
^ dadUKch marked that they contain an organic solvent. . '! i .1 l8. Process for dyeing and printing fully synthetic organic fibers, characterized in that
I free of sulfo groups / ; ! man / dyes of the formula j N-N! ³ ^ -O ■ ·! ■ C. j [where R, and Rp are optionally substituted alkyl groups, which may be interrupted by heteroatoms, and R,
! and Rp '"■ - · together with the one on the aromatic nucleus any nitrogen atom can form a 5- or 6-ring ^ 'X is an NH group or an oxygen atom and R is J is / ; , organic residue / used. · 19 · The method according to claim 18j, characterized in that that you dye fibers made of linear polyester or cellulose - 2 1/2 - acetate. 309843/1090 CIBAGEIGYAG 23192 3JD 20. Process according to Claims 18 and 19 / characterized in that the dyes according to Claims 2 to 6 are used. \ , 21. The obtained according to claims 18 and 19 i dyed fiber material. 309843/1090