DE1569699B2 - Water-insoluble styryl dyes and their use for dyeing fibers containing ester groups, polyacyl fibers or for pigmenting high molecular weight organic material - Google Patents

Description

The present application relates to new, valuable, water-insoluble styryl dyes of the formula ..

NC R ₁ . R ₂ CN

C = CH-Ai-NR ₃ -ZR ₄ -NA ₂ -CH = C Älhylcarbamyioxy can be substituted, mean, Z is

IO

-Ο—

-S— -NH-

C ₁ -C ₃ alkyl
-NH-CH ₂ CH ₂ -NH-

—N— '

-N-CH ₂ CH ₂ -N-

CH ₃ CH ₃

- O — CH ₂ CH ₂ —NH- CH ₂ CH ₂ -

-O

or the radical of the formula '—Ό-R ₅ - O -, in which R ₅ door' branched ■ '. oder..chain-shaped, aliphatic divalent hydrocarbon radicals with 2 to H) Kph-. lehstoffatomeri, remnants of the formulas. '... ....: ... _: '',. .

-CH ₂ CH ₂ -0-CH ₂ CH ₂ -Υ ""; v _

-CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ Ch ₂ -

the phenyiaraliphatic hydrocarbon radicals with 7 to 15 carbon atoms mentioned in the description, phenyl aromatic hydrocarbon radicals with 6 to 15 carbon atoms, and cyclohexylene Z is also the divalent radicals of the formulas

-C-O-

-0 — c— —o — c — o—

wherein Ai and A ₂ 'unsubstituted or by lower alkyl, lower alkoxy, halogen, phenoxy, thiophenoxy-trifluoromethane / acetylamino or amihocarbonyl substituted p-phenylene groups C R] and R ₂ hydrogen,' if necessary. substituted alkyl of one to four carbon atoms; where halogen, hydroxy, methoxy, ethoxy, cyano, phenyl, acetoxy, cyanoethoxy, cyanoacetoxy, benzoyloxy ,. Ethylcarbamoyl, Pheriylcarbarnpyl come into question, sbSvie /; - Carbo (methoxy-, ethoxy- or propoxy) ethyl (whereby the terminal alkyl group in r; / - Stelluiig can carry cyano or an Äminogrupppe), ' ßr \ pdef ^ y- £ arb > o ₇ (rnethoxy- *; öder'äthöxyjpröpyl, 'tl- (Acety \ - qdef; FoK mylJ-amihbäthyJ ^' / iA ^ etöxyätnyl ,; ^
pyl, / i-MethariSulföiiyläthyl-, Γ / ^ Ätnansulfonyiäthyl, '/ ;-( p-Ch! orbfenzolsujfönyl) ä (hyli'_;'/ i-Methylcärbarnyl-. oxyäthyi ,, ^ -iHeriylcarbärnyloxyäthyi, ^ - (äthoxyoxyäthyi, ^ - (äthoxyoxyäthyi, - öcief -isppröpylöxy ^ carbonyloxyät ^^ j '^ cetamidopröpyl ^' ^ :( p-NJtrbRheiipxyj-ät ^
droxy'pl ^ nöxy j ^ thy 1; ^; '': V ^ - ^^

ethyl, / iO / 'r (Cyänpv Hydrpxy-, 1 methoxy- or, Aceü _: oxy) -ätHo ^ ycarbonyl] -äthy 1,' ^ - Carboxyatji \ y \, y-Ami-; n9prbpyl, ^ ₇ diethyiärhinoäthyl, / i -cyandcetoxyäthyj- ,; Benzyloxyäthyriind p _: Aikoxy- or PKenpxybenzpyl-; oxyäth'yr means ^; p'der. with A, or A ^^^^ Tetra- .; methyl - 1,2,3,4 - 'tetrahydrocholine, 7 -j. Methyl 1,2 ,: 3,4-tetrahydrochinoline or! ^^, ^ - tetrahydrochino-. form lin; R ₃ 'and R4 are alkylene groups with bi $; 4 carbons _; lenstoiTatbrnen, soft by hydroxy, acefqxy or ·

O O O

—CO — NH-CO- —NH-CO -— CO — NH- :; -. - Q — CO — CO — O—: - ;: —CO —NH — NH — CO /,:;

-NH-co-CO ^ -NH-:; ; ; :; ;

.or

—X' — Z'— X'—

represents wherein X '= - O or imino and Z' is the acyl radical of an organic dicarboxylic acid having 3 to 16 carbon atoms, an organic Dicarbamiri- ^'1 acid having up to 15 carbon atoms, a radical of the formula - OCO - X' -R ₆ -X '- OCO - is where R _{6 is} an aliphatic / or phenylene aromatic radical having 2 to 10 carbon atoms; or, if R ₃ and R ₄ are formed by opening oxirane rings, optionally by aliphatic carboxylic acids with up to 3 carbon atoms or ethyl or; Phenylcarbamic acid esterified Ν, ^ - hydroxy-ethyiene or -propylene groups, are an aliphatic or phenylaromatic radical with up to 15 carbon atoms, which is optionally bonded on both sides via. - O - - and Yi and Y ₂ ', cyano , CC ₄ alkoxycarbonyl or phenylsulfonyl groups are .'_,,. ^: ;:; ; -, ·;:.:.,:;

The new dyes can be used, for. B. reverberate if man cnlneither

a) the dyes of the formulas.

NC

Y ₁

NC

Y ₂

C = CH-A ₁ -NR ₃ -X ₁

R ₁

C = CH-A ₂ -NR ₄ -X ₂

and when η = I, Y 1 ′ and Y ₂ ′ together with Z form an additive diepoxy compound.

In the preparation it is possible to use the same components A ₁ , A ₂ , Ri and R ₂ as well as R. and R ₄ , so that symmetrical bis-styryl dyes are obtained, as well as starting materials in which one or more of these components are different are from each other, so that one leads to asymmetrical styryl dyes !! got.

Examples of the radicals A) and A ₂ are 1,4-phenylene groups of the formulas

C ₁

y ν

where X ₁ and X _{2 represent} a group containing at least one reactive hydrogen atom, preferably an amino, mercapto or hydroxyl group, or their reactive derivatives and Ri, R ₂ , R ₃ and R _{4 are} optionally substituted alkyl or alkylene groups and A ₁ , A ₂ , Y ₁ and Y _{2 have} the same meaning as above, with a _{bifunctional compound free of SO 2} groups to give the dyes of the formula (I) according to the invention or

b) the dialdehyde of the formula

'■ OCH-A ₁ -NR ₃ -ZR ₄ -NA ₂ -CHO

or its aldimine with a cyano compound of the formula

NC

CH ₂

condensed in a molar ratio of 1: 2 or

c) the monostyryl dyes having a reactive hydrogen atom bonded to an amino group of the formulas

NC

\> '· ■■■

C = CH-A ₁ -NH-R ₁

NC

, C = CH TA ₂ ^ NH ¹ TT-R ₂ ., ^:

· ■ / ■

with a bifunctional compound of the formula

converts, where / i is an integer in the value of I or'2 and Y, 'and Y ₂ ', if η - 2, each a reactive negative Res !, preferably a; Halalom. is

called, where Cj, C ₂ , d! and d are ₂ hydrogen atoms, halogen atoms, in particular chlorine or bromine atoms, lower alkyl groups such as methyl or ethyl groups, lower alkoxy groups such as methoxy or ethoxy groups, thiophenoxy or phenoxy groups.

The groups C ₁ and C ₂ are preferably bonded in the ortho position to the C =C double bond and, in addition to the preferred groups mentioned above, can also contain a trifluoromelhyl group, an alkylsulphonyl, preferably a methylsulphonyl group, and an optionally alkylated on the nitrogen atom, e.g. B. methylated, acylamino group in which the acyl radical is the remainder of an organic monocarboxylic acid, an organic monosulfonic acid, such as methane, ethanoic or p-toluene monosulfonic acid, or the remainder of a carbamic acid or a carbonic acid monoester or mohoamide, such as phenoxycarbonyl, methoxycarbonyl and arhinocarbonyl.

The groups dj and d ₂ are preferably bonded in the ortho position to the coupling-directing amino group! ",; __ '..., ..'.: .. ', -) \'} ',. i ■' .. ■: ■ .- ^: ',

The groups R ₁ and R ₂ can mean hydrogen atoms, alkyl groups or substituted alkyl groups, such as ^ chloroethyl, //, //, // - Trifiüoräthyi-, //, j'-dichloropropyl-; // - Cyänälhyl-, // - Ethoxyäthyl- or - / - Methbxybutyl-, // - HydroxyäthyK, '//,; - Dihydroxypropyl-, // - Nitröäthyl-, // - CarboimethÖxy-,' älhoxy- or propoxyj- ethyl (whereby the terminal alkyl group in the f> / - position can carry cyario ^, carbalkoxy, acyloxy and amino groups ^,! β- _Ί or y-carbp- (methoxy- or ethpxy) -propyl-, // - ( Acetyl- or FprmylJ-aniirio-ätHyl-i; // - Acetyloxyathyl - ^ / A ^ -DiacctoxypropyI- ^,! // - Methanesulfonylät h'yl-,; '// _: Äthan.sulfphyläthyl-V or // - (pyChlorbenzplsulfonylj -äthyl-, / '' - Mcthyicarbärnylöxyäthyl-, and // - Phcnylcarbarnyloxyäthyl-, ¹ // - (Methpxy-; ethoxy- or -isopropylpxyj-carbonyloxyäihyl-, ^ -Äcelamidopropyl-, // - (p-Niirophcrioxy) -ethyl -, '7 / - (p-Hydroxyphynoxy) -äthyl-, // - (/ «' - Acetylethoxycarbonyl) -äthyl-, // - [// '- (Cyano-, Hydroxy-, Mclhoxy- or AcctoxyJ-alhoxycarbonyl -ethyl-. Cv-

analkoxyalkyl-, // - carboxyiilh} I-. , ·; - Accl \ la'lhyl-. —Aminopropyl, // - diethylamino oil! -. // - cyanoaceloxyalhyl and / j-benzoyl- / i '- (p-alkox) - or phenoxybenzoyl-oxyethyl groups. The groups R ₁ and R ₂ generally contain at least 2 carbon atoms and no more than eight, preferably no more than six, carbon atoms.

If the groups R and / or R ₂ with the adjacent phenylene groups A] or A _{2 are to form} a hydrogenated heterocyclic ring, one gehl z. B. of Tctrahydroquinoline derivatives as components of the formulas

ί ^ι \

HA ₁ -N-

Η —Α, —Ν

15th

20th

HA ₁ -NHR ₁ and HA ₂ -NHR ₂

- Ο— —S-

-NHCH ₂ CH ₂ NH
N CH ₂ CH ₂ -I
/ CH.,: CU)

C) CH ₂ CU ₂ NU
R ₅ -

NH-

CU, CH, ./Ο-

25th

the end. For example, 2,2,4,7-tetramethyl-1,2,3,4-telrahydroquinoline and 7-methyl-1,2,3,4-tetrahydroquinoline are suitable.

The groups Rj and R ₄ are optionally substituted alkylene groups with preferably at least two carbon atoms, such as. B. unsubstituted ethylene groups or, gcma'ii a particular embodiment of the invention, in // - position to the amino group hydroxylierle alkylene groups. The latter arise, for example, from the two-sided reaction of diepoxides, in particular diglycidyl compounds, with the components carrying at least one reactive hydrogen atom

or the corresponding styryl dyes !!. The hydroxyl groups formed in the // position can be substituted, and the substitutes together with the oxyethyl groups leading to the N atom can have the same meaning as the groups R ₁ and R ₂ defined above, insofar as they differ from one of the N atom Derive outgoing N-Oxyäthylgruppc.

For the colorless bridge, groups of the following formulas come into consideration:

where R * is one of the divalent aliphatic, arali-

phatic or aromatic residues of animal formula

cn, --cn, · -

-CH,

CH, -

// V

CH;

// V

// V

CH,

and especially the groups containing acyl radicals Formulas

- OCO-

- OCOCOO-

- CONH-— CONHNHCO -

-OCOO- ^

- NHCO -— CONHCO—
- NHCOCONH

as well as the colorless link of the formula
- X'CO —R "—COX'-

wherein X 'is an oxygen atom, a sulfur atom or a -NH- group and R ,, is an aliphatic aromatic or heterocyclic radical. the colorless link of the form

- X '- CO - NH - R ₇ -NH - ■ CO - X' -

wherein X ″ is an oxygen atom, a sulfur atom or an NH group and R _{7 is} an aliphatic, aromatic or heterocyclic radical of a diisocyanate, preferably an ethylene, hexamethylene, p-phenylene or toluene radical, a radical of the formula

CH-

is, the colorless link of the formula
- OCOX-R "-X '- C) CO

wherein X 'has the same meaning as above and R _{K is} a divalent organic radical, in particular an aliphatic araliphatic aromatic or

M) -.heterocyclic! Residue. Is. which can be interrupted by groups X 'if X' is an NH group . Rn has the same meaning as R- ..

/.ur. Hinfiihrung of the link Z to gehl as follows: ·; .- ■ · _ν:; '..

h5 The linkage takes place via dicarboxylic acid esters according to known methods, e.g. B. by esterification, in particular with a / coliopic dehydration, by Umeslerung with elimination of a volatile one

809 522/6

Alcohol or phenolic oiler by Umsel / img with Dicurbonsäurcaiihydriden, by reaction with dicaibonic acid halides. where the on the phenylene radical A tertiary amino group present serves to take up the hydrogen halide released can. For the preparation of the [^ carbamic acid esters, if the group X is a hydroxyl group is, with diisocyanates, preferably either in inert solvents or Heals without solvents at moderate temperatures, but also use active solvents can.

The class of organic acid chlorides also includes phosgene, with which the carbonates are made receives; the reaction can be carried out in such a way that the hydroxyl group of the dye component is removed initially reacted with at least one mole of phosgene to form the chlorocarbonic acid ester and this on Adds diol or unsubstituted or partially substituted diamine. You can use the carbonic acid esters however, they can also be prepared by transesterification with dialkyl or diaryl carbonates.

When X is an amino group having at least one active hydrogen atom, it is preferably obtained the corresponding dicarboxamides by reaction with dicarboxylic acid halides.

When Z is the remainder of a dicarboxylic acid, the starting materials are bifunctional reaction components for group X the following free acids, their halides and anhydrides (if the acid is

HOOC

HOOC

HOOC

HOOC

As diisocyanate components Z ', which by reaction with 2 moles of the dye component of the formula

Anhydride formation is capable) or their esters with volatile alcohols in question:

Oxalic acid,;

Succinic acid, ''

Malonic acid.

Pimelic acid.

Adipic acid,

Methyl adipic acid,

Azelaic acid,

Sebacic acid,

Maleic acid,

Fumaric acid,

Allyl succinic acid,

Dodecy! Succinic acid,

Diglycolic acid,

Methylene-bis-thioglycolic acid,

2,3-dibromosuccinic acid,

Thiodibutyric acid,

Tetrahydrophthalic acid,

Hexahydrophthalic acid,

Endomethylenetetrahydrophthalic acid,

Methylenendomethylenetetrahydrophthalic acid,

Hexachloroendomethylenetetrahydrophthalic acid,

Phthalic acid,

Isophthalic acid,

Terephthalic acid,

2,5-thiophenedicarboxylic acid,

Furandicarboxylic acid,

the dicarboxylic acids of the formulas

COOH

COOH

NC

C = CH-A ₁ -NR ₁ -R ₃ -X

where X is an amino, mercapto or hydroxyl group that form the colorless link Z are suitable as aliphatic, araliphatic or aromatic diisocyanates, the

. Hexamethylene diisocyanate,
N, N'-bis (4-methyl-3-isocyanato-phenyl) -ur-

Toluene-2,4- or -2,6-diisocyanate or a mixture thereof,

Phenylene-1,4-diisocyanate,
Diphenyl 4,4'-diisocyanate,
Diphenylmethane-4,4'-diisocyanate,
Diphenyl-dimethylmethane ^^ '- diisocyanate,

COOH

Stilbene-4,4'-diisocyanate,

Benzophenone 4,4'-diisocyanate,

Diphenyl ether or diphenyl sulfide diisocyanate, as well as their substitution products, e.g. B. with alkyl, alkoxyl,

so halogen or nitro groups substituted derivatives, such as. B. 3,3'-dimethyl or 3,3'-dimethoxy or U'-dichloro-diphenyl-methane ^^ '- diisocyanate.

Symmetrical diisocyanates such as diphenyl-4,4'- or diphenylmethane-4,4'-diisocyanate are preferred used.

The diisocyanates can optionally also be prepared in situ, e.g. B. by implementing Bis-chloromethylbenzenes and sodium or lead cyanate in active solvents.

To produce carbonates, if X is a hydroxyl group, either directly with phosgene, optionally in the presence of quaternary ammonium bases or salts, to convert to the carbonate or can first produce the chloroformic acid ester of a styryl dye residue and either with the the same or a further styryl dye radical containing a free hydroxyl group to the carbonate realize.

il

As suitable divalent aliphatic, cycloaliphatic, araliphatic or aromatic hydroxyl compounds, their hydrocarbon structure is given if is interrupted by heteroatoms, for example, the following hydroxyl compounds are a'.nge-Rihrt:

1,2-dihydroxyethane,

1,2- or 1,3-dihydroxypropane,

1,2- or 1,3- or 1,4- or 2,3-dihydroxybutane, 1,2- or 1,3- or 1,4- or 1,5- or 2,3- or 2,4-dihydroxypentane, the corresponding dihydroxyhexanes, -heptanes, -octanes, -nonanes, -decanes, -undecane, -dodecane, -hexadecane, -octadecane,

1,4-dihydroxybutene,

US dihydroxy ^ dimethylpentane,

Di - (/ miydroxy-ethyl) -thioether,

Di- (p'-hydroxy-ethyl) -ät, her (= diglycol),

Triglycol,

Cyclohexanediol-1,2 or -1,3 or -1,4,

4,4'-dihydroxydicyclohexylmethane,

4,4'-dihydroxydicyclohexyldimethylmethane,

4-hydroxybenzyl alcohol,

1,4-Di - (/ ^ - hydroxy-ethoxy) -benzene,.

1,2- or 1,3- or 1,4-dihydroxybenzene,

1-methyl-2,4- (or 2,3- or 3,4- or 2,6- or

2.5- or 3.5-) dihydroxybenzene,
M-dimethyl ^ S-dihydroxybenzene,
l-ethyl-2,4-dihydroxybenzene,
l-isopropyl ^ -dihydroxybenzene,
4,4'-dihydroxyazobenzene,

2,4- or 4,4'-Dihy'droxydiphenyläther,
2,2'-dihydroxyethylene glycol diphenyl ether,

2,6- or 2,7-dihydroxynaphthalene,
4,4'-dihydroxydiphenylamine,

2,4'- or 4,4'-dihydroxydiphenyl,
4,4'-dihydroxydiphenyimethane,
4,4'-dihydroxydiphenyldimethylmethane,
1,1'-Di (4'-hydroxyphenyl) -cyclohexane,
4,4'-dihydroxydiphenyl (di) sulfide,
4,4'-dihydroxydiphenylsulfonyl or mixtures of such diols.

The introduction of ether bridges or the remainder - O - R ₅ --O - takes place z. B. by reacting aqueous or alcoholic solutions of alkali phenolates with dihalides. If dichlorides are used as the starting point, dihalides with active chlorine atoms can in particular also be used. Suitable dihalides are e.g. B. 1,4-dichlorobutene, di-ß-chloroethyl ether, dichloroethyl formal and the isomers of bis (chloromethyl) benzene.

If you put the dyes of the formulas

Thiol, carboxyl or, in particular, amino groups, with a diepoxide, are obtained as terminal Groups of the bridge member Z are ethyl, thioether, ester or imido bridges, and at the same time in / ^ - position to the two terminal carbon atoms each a hydroxyl group is formed which created by opening the epoxy rings.

A particularly preferred way of preparing the —R ₃ —Z — R ₄ - group consists in the mutual linkage of the styryl dye of the formulas having at least one active hydrogen atom on the coupling-directing nitrogen atom

NC R ₁

C = CH-A ₁ -NH
Y ₁

and

NC

C = CH-A ₁ -NR ₃ -X ₁

Y ₁ ^:; '" R ₁ ''

NC

C_1_ ^ t τ —rV-ΓΊ.

NC

C = CH-Α, -Ν -Η

or p-amino-phenyl radicals of the formulas

HA ₁ -NH-R ₁ and HA ₂ -NH-R ₂

with a Diepoxydverbindungen, as z. B. be used commercially in epoxy resin chemistry. If a diglycidyl compound is used, a compound is obtained in which the symbols of the group - R ₃ - Z - R ₄ - have the following meanings: R ₃ and R ₄ are propylene groups which are in the / S position of the para position Nitrogen atom have a hydroxyl group, and Z is the residue of a diglycidyl compound depleted of the glycidyl groups. Accordingly, the invention preferably relates to bisstyryl dyes of the formula (1) which are characterized in that the group

R ₃ ZR ₄

wherein X ₁ and X _{2 are} each a reactive hydroxyl, by addition of a diepoxide to two coupling components or azo dye residues having at least one active hydrogen atom on the coupling-directing nitrogen atom.
The conversion of amino groups located on the aromatic nucleus forms one of the basic reactions in epoxy resin chemistry and has therefore been studied in every respect, e.g. B. in the works of Lee and Neville, "Epoxy Resins", New York, 1957 and 1967, and: Ho ab en —We yl, "Methods of Organic Chemistry", Volume 14, Part 2, Stuttgart, 1963, pp. 462 to 567 have been dealt with in detail, as well as the reaction with other functional groups and the usual diepoxides of epoxy resin technology are described there.

The reaction of epoxy groups with amino groups can take place at room temperature, however, amino groups on the aromatic nucleus will be reacted at temperatures of 30 to 150.degree.

The implementation is done in such a way that the two Epoxy groups of the formula

-C

with the free amine hydrogen of the group of the formula ¹ H - NR - to the / J-Hydroxyamine of the formula

C — CH-NR-

OH

reacts, where R is one of the radicals Rj or R ₂ . The hydroxyl groups formed by the opening of the 1,2-epoxy rings can subsequently be substituted, in particular acylated; together with the ethylene bridge of the formula shown above leading to the para nitrogen atom, they can have the same substituents as the alkyl groups R] and R ₂ , which are derived from an N-ß-hydroxyethyl group, but in particular the radicals of aliphatic carboxylic acids, such as acetic acid, propionic acid, etc. the residues of aromatic carboxylic acids, such as benzoic acid, and alkyl or arylcarbamyl residues, such as ethylcarbamyl or phenylcarbamyl residues.

Bisslyryl dyes that differ from a C, N-diglycidyl-alkylamine as a milk component

R3 L 1x4

derive, such as B. N.N-diglycidylpropylamine, can one also obtained by adding an alkylamine with twice the molar amount of a styryl dye general formula

NC

C = CH-AN (R) -CH ₂ -CH (UH) -CH ₂ -X

converts, in which X is a labile negative radical, in particular a halogen atom, or by using equivalents Amounts of a dye of the formula

reacts differently and before or after the fourth group R ,, with an alkylating agent R ,, - X condensed on the quaternized nitrogen atom, where X is an easily split off negative radical, like him is used for alkylation reactions, especially a chlorine, bromine or iodine atom.

Examples of the well-known class of epoxy resins include:

Butadiene diepoxide, the diglycidyl ethers of dihydric alcohols, such as glycol diglycidyl ethers, the diglycidyl ethers dihydric phenols, such as 4,4'-dihydroxydiphenylmethane, -dimethylmethane or -sulfone, the diglycidyl ethers from polyvalent thiols, such as bis- (mercaptomelhyl) -benzenes, the N, N'-diglycidyl compounds, z. B. of N, N'-dimethyl-4,4'-diaminodiphenylmethane, ethylene urea or oxamide, and the diglycidyl esters of aliphatic, cycloaliphatic or aromatic dicarboxylic acids, such as phthalic acid, Hexahydrophthalic acid, tetrahydrophthalic acid or succinic acid.

The dialdehydes of the formula

R,

OCH-A ₁ -NR ₃ -ZR ₄ -NA ₂ -CHO

in which A ₁ , A ₂ , R ₁ , R ₂ , R ₃ , R ₄ and Z have the same meaning as in formula (1), are advantageously obtained by condensation of a diamine of the formula

HA ₁ -NR ₃ -ZR ₄ -NA ₂ -H

with dimethylformamide and phosphorus oxychloride according to V i 1 s m e y e r and hydrolysis of the intermediate product obtained.

The starting materials used are preferably dialdehydes of the formula given in which Z is a Oxygen or sulfur atom, an imino group or one of the groups

C = CH-A ₁ -N (R ₁ J-CH ₂ -CH (OH) -Ch ₂ -NH-R ₅

and the dye of the formula

■■■ nc - "" · ' ^: "■' ■■: [■ '- ■' ■ / ^:

■ (■ • ■ - (■ ^h:; -a ^{_'2 -,} -N (R ₂₎ - (- h ₂ -c: h (c) H) -CH ₂ -X

- COO— -OCOO—
0-R ₅ -O- ^: --NH - R ₅ -NH- ■

- OCONH - R ₅ - NHCOO -

- CONH - R ₅ -NHCO -

- NHCO-R ₅ -CONH-

denotes in which R ₅ denotes an optionally substituted alkylene or phenyl group, but in particular b ¹ ) dialdehydes in whose Z at least one acyl group belongs or, by reacting 2 moles of aromatic amine with 1 mole of dicpoxide, X has the same meaning as above - that is.

Examples include the following dialdehydes are listed:

CH ₃ KJ

OCH- ^ f ^ -NC ₂ H ₄ -NC ₂ H ₄ -N CHO

C ₂ H

2 "5

C, H

2 "5

OHC / ^ NC ₂ H ₄ OC ₂ H ₄ -N / V CHO

C ₂ H ₅ C ₂ H ₅

OHC- ^ VNC ₂ H ₄ OC ₂ H ₄ -N- ^

CH,

CH,

OHC

CH ₃ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂

CH,

and the dialdehydes of the formula

C ₂ H ₅ C ₂ H ₅

OHC

y VNC ₂ H ₄ -Z-C ₂ H ₄ -N-y 1-S-CHO

CH ₃

where Z has the following meaning: —O— —S—

-NH-

—N—

I.
Alkyl

-OCH ₂ CH ₂ O- -N-CH ₂ CH ₂ N-

CH ₃ CH ₃

CH ₂ O-

-OCO- -OCOO- - ^: () C () NHCH ₂ CH ₂ NHCOO.-TCONHCO- -CONHNHCO

Ci) NH

NHCO CH ₃

-NHCO

CONH-

O- -o-> ~ ^

CH,

• V-O-

CH ₃ OCOCOO

w, OC NH ^ / CH ₂ <(

NH CO

OCONH / / NHCOO

NIIC (KH ₂ CH ₂ CONH

O C NH (CH,), NH C

I! · "Il

ο O

NHCOCONH

17th

Also the dkildehydes of the formulas

18th

C ₂ H ₅

CH,

OHC

CHO

OHC

CH ₅ H ₅ C- ■ NN

V ₂ H ₄ -OC ₂ H ₄

CHO

Suitable dialdehydes, which in // - position to the coupling-directing nitrogen atom each have a secondary, optionally have acylated hydroxyl group are, for. B .:

C ₂ H ₅ -CH -CH ₂ -N-CH ₂ H ₅ C
N- . N- -CHO CH ₂ - OH CH -CH-CH ₂ < CH ₃ CH ₃ OH CH ₅ -CHO >

CH ₂ -CH-Ch ₂ -N-CH ₂ -CH-CH ₂ O CH O

I / \ I

CO CH ₃ CH ₃ CO

CH ₃ CH ₃

Suitable dialdehydes which contain at least one acyl group in the bridge member are ζ. Β .:

C ₂ H ₅ H ₄ C ₂

N O Ν -C> -CHO

ι — Ο - C— O-

CH ₃ CH ₅

CH ₁

OHC

-N

H ₄

O N ~ / V-CHO

NH-CO-QH ₄

CH ₃

CH ₅

OHC

H ₅ C,

OHC

CH ₄ CN NCH ₄ C

N O ON

\ Il Il /

CH ₄ -OC- (CHA-COC ₂ H ₄

CH ₃ .

-CHO

Malonitrile, methyl, ethyl, propyl, isobutyl or ϊ-cyanoethyl ester, cyanoacetamide and phenylsulfonylacetonitrile may be mentioned as cyano compounds of the formula NC - CH _{2 - X.} v.

The condensation of the dialdehydes with the cyano ^r > connection is expediently carried out in the heat in the presence of a basic catalyst, such as. B. ammonia, dimethylamine, diethylamine, piperidine, piperidine acetate, sodium or potassium alcoholate, optionally in the presence of a solvent such as. B. methanol, ethanol, benzene, toluene, xylene, chloroform or carbon tetrachloride. If solvents are used, the water formed during the reaction can be continuously removed from the reaction mixture by azeotropic distillation of the latter, as a result of which the reaction equilibrium is constantly shifted in favor of the condensation product. The condensation can also take place without basic catalyst in glacial acetic acid or another organic acid or in the absence of a solvent by melting the reaction "tion subscriber in the presence of a basic catalysis φ crystallizer, for example ammonium acetate or piperidine acetate.

Instead of the aldehydes, their aldimines, d. H. their condensation products with primary Amines, in particular aminobenzenes, so so-called Schiff bases of the formula

RN = CH-A ₁ -NR ₃ -ZR ₄ -NA ₂ -CH = NR

(4)

30th

35

can be used as starting materials. In the formula given, R preferably denotes a benzene radical, for example the phenyl or a sulfophenyl radical. The compounds of the formula (4) can be obtained are caused by condensation of the action product of formaldehyde and hydrochloric acid on the Amine of formula (3) with a nitrobenzene, for example nitrobenzenesulfonic acid in the presence of iron |, and hydrochloric acid according to Example 17 of US Pat. No. 25 83 551.

Compared to the bisstyryl dyes described in French patent specification 14 49 542, in which the dye residues _{are connected via an —SO 2} bridge, the dyes according to the invention are distinguished by significantly better drawing ability on polyester fibers. "

The new dyes are extremely suitable, especially after being converted into a finely divided one Shape, e.g. B. by grinding, pasting, falling over, etc. for dyeing and printing hydrophobic synthetic and semi-synthetic fibers, for example made of cellulose acetate, but in particular aromatic polyesters. Even the hydrophobic ones Fibers made from copolymers of propylene oxide and unsaturated epoxies and fibers on polyvinyl chloride ed. Basis can be colored with the new dyes.

It is obtained on hydrophobic fibers, in particular on polyester fibers, after the usual dyeing; drive, e.g. Example, of a dye liquor containing a fine dispersion of the dye and suitably a dispersant, at temperatures up to close to 100 ⁰ C, optionally with the addition of a swelling agent, or at temperatures above 100 ° C under application of over pressure, pure strong, greenish yellow colorations, which are characterized by excellent light and sublimation fastness. The new dyes also have the advantage of only slightly staining wool and other fibers in the dyebath. They are therefore well suited for dyeing polyester-wool or z. B. polyester-triacetate blend fabrics.

The dyes according to the invention are also suitable for dyeing by the so-called thermosol process, according to which the material to be dyed with an aqueous dispersion of the dye, which advantageously contains 1 to 50% urea and a thickener, in particular sodium alginate, preferably at temperatures of at most 60 ⁰ C is impregnated and squeezed off as usual. It is expedient to squeeze in such a way that the impregnated goods retain 50 to 100% of their initial weight in dyeing liquid. To fix the dye, the fabric so impregnated, expediently after prior drying, for. B. in a warm air stream to temperatures of over 100 ⁰ C, for example between 180 and 210 ⁰ C, heated.

The just mentioned thermosol process for dyeing blended fabrics is of particular interest made of polyester fibers and cellulose fibers, especially cotton. In this case, the padding liquid contains in addition to the dye according to the invention, dyes suitable for dyeing cotton, for example Vat dyes. When using the latter, a treatment of the padded fabric is required heat treatment with an aqueous-alkaline solution of a reducing agent commonly used in vat dyeing necessary.

Some of the new dyes are also valuable pigments which can be used for a wide variety of pigment applications, e.g. B. in finely divided form for the dyeing of rayon and viscose or cellulose ethers and esters or of superpolyamides or super-polyurethanes or polyesters in the spinning mass, as well as for the production of colored lacquers or lacquer formulas, solutions and products made of acetyl cellulose, nitrocellulose, natural resins or synthetic resins, such as polymerization resins or konderization resins, e.g. B. aminoplasts, alkyd resins, phenoplasts, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, rubber, casein, silicone and silicone resins. _: '. _; ,] .

In the following examples, unless otherwise stated, the parts are parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

': Example II?

, 48.8 parts of N-ethyl-N - (/ 3-oxyethyl) -m-toluidine in 30 parts by volume of dry benzene are mixed with 11 parts Sodium metal is stirred under reflux for 15 hours, excess sodium is removed and then 53.8 parts of N-ethyl-N - (/ 3-chloroethyl) -m-toluidine added in 50 parts by volume of dry benzene and 4 parts of sodium iodide. The mixture will refluxed for a long time with stirring, then diluted with dry benzene. From the resulting Sodium chloride and sodium iodide are filtered off, the filtrate is concentrated and distilled. It boils between

185 and 195 'at 0.1 torr. The amine thus obtained corresponds to the formula

C ₂ H ₅ C ₂ H ₅

NC ₂ H ₄ -OC ₂ H.

Addition of ice neutralized with concentrated sodium hydroxide solution at room temperature. The chloroform phase is washed once with water, then dried _{with Na 2} SO _4. After the chloroform has been distilled off, the crude dialdehyde of the formula remains

CH,

Analysis:

Calculated ... C 77.6, H 9.5, N 8.2%;
found .... C 77.9, H 9.7, N 8.3%.

The same amine was obtained by reacting 2,2'-dichloro diethyl ether with N-ethylm-toluidine.

10.2 parts of this amine are added at 15 to a mixture of 1.1 parts by volume of dimethylformamide with stirring and 9.4 parts by volume of phosphorus oxychloride entered and then stirred for 6 hours at 60 ". The reaction product is then poured onto ice chloroform is added and the mixture under

IO

15th

CH ₅

Γ Γ

NC ₂ H ₄ -OC ₂ H ₄ -N

CH,

CH,

back as dark oil.

4 parts of this dialdehyde are in 25 parts by volume of absolute ethanol with 1.6 parts of malonitrile and 0.2 parts by volume of piperidine are added and the mixture is refluxed for 5 hours. When cooling to room temperature a dark oil is produced which becomes crystalline when standing. After recrystallization, the fine, orange-yellow crystals of the dye of the formula

NC

NC

CH,

= CH

NC ₂ H ₄ - O — C ₂ H ₄ -

CH = C

CH ₃

CN

CN

Analysis:

Calculated ... N 17.1%;
found N 17.1%.

It dyes polyester fibers in pure greenish yellow tones with excellent lightfastness and sublimation fastness.

Staining instructions

1 part of the dye obtainable according to Example 1 is mixed with 2 parts of a 50% strength aqueous solution of the sodium salt of Dinaphtbylmethandisulfonsäure wet ground and dried

This dye preparation is mixed with 40 parts of a 10% aqueous. Solution of the sodium salt of N - benzyl - // - heptadecyl - benzimidazole disulfonic acid and 4 parts of a 40% acetic acid solution admitted. A dyebath of 4000 parts is prepared from it by diluting it with water.

In this bath you go at 50 "with 100 parts one cleaned polyester fiber, the temperature increases to 120 to 130 "and in half an hour stains for one hour in a closed vessel at this temperature. Then it is rinsed well. You get a greenish yellow color with excellent lightfastness and sublimation fastness.

Example 2

If the starting material used is the dialdehyde of the formula

35

OCH NC ₂ H ₄ -OC ₂ H ₄ -N

C ₂ H ₅

/ V

CHO

and proceeding as indicated in Example 1, a dye is obtained which also contains polyester fibers dyes greenish yellow shades of very good lightfastness and sublimation fastness.

Example 3/1

"v!

4 parts of the dialdehyde described in Example 1 are in 25 parts by volume of ethanol with 2.4 parts of cyanoacetic ester and 0.2 parts of piperidine refluxed for 4 hours. 3.5 parts are obtained on cooling of an orange powder of the dye of the formula

NC

C ₂ H ₅ OOC

, QHs

C = CH

CH,

C ₂ H ₄ -OC ₂ H ₄

CH = C

CH ₃

CN

COOC ₂ H ₅

In this way, greenish-tinged yellow colorations with good fastness properties are achieved on polymeric materials. Table I below contains a number of other valuable dyes of the general formula

■■■ :: ■■ · NC ^ ¹¹ R ₁ ¹ R ₂ ' Ϋ "^' CN

Y ₁

. (■

-NR, ZR ₄ -N-

which are obtained in a manner analogous to that in Example 1.

- C

Tabel

example

23

24

CH ₃
CH ₂
C ₂ H ₅

Il

-C ₂ H ₄ OCCH ₃

-QH ₅

-C ₂ H ₄ OCH ₃

-C ₂ H ₅

-C ₂ H ₅
-C ₂ H ₅

-C ₂ H ₅ -CH _:

-C ₂ H ₅ -C ₂ H ₅

-C ₂ H ₄ OCCH ₃

-C ₂ H ₅

-C ₂ H ₅

-C ₂ H ₄ OCH ₃

-C ₂ H ₅

"C ₂ H ₅ -C ₂ H ₅

C ₂ H ₄ - C ₂ H ₄ C ₂ H ₄ CH ₂ -CH-CH ₂ -QH ₄ C ₂ H ₄ - OCNHC ₂ H ₅ / ~ i IT C ₂ H ₄ - -C ₂ H ₄ C ₂ H ₄ Il
O -C ₂ H ₄ C ₂ H ₄ - C ₂ H ₄ C ₂ H ₄ - -C ₂ H ₄ C ₂ H ₄ -C ₂ H ₄ C ₂ H ₄ - -C ₂ H ₄ —H2 CH CHj 0
Il -C ₂ H ₄ Il
OCCH ₃ -C ₂ H ₄ 1

-CH,
-H

-CH ₃
-CH ₃

-H
-H
-H
-H
-H

-Cl
-H

-H
-H

-H
-H

-OCH ₃

-H

-H

-H

-H

-H
-H

Table I (continued)

at
game C ₂ d ₂ Y ₁ Y ₂ Z CH ₃ colour 1 -CH ₃ - Η -CN —CN -O- greenish yellow 2 YY - Η -CN —CN -O- CH ₃ greenish yellow 3 -CH ₃ YY -CN —CN greenish yellow 4th -CH ₃ —Η -CONH ₂ -CONH ₂ greenish yellow 5. - Η -OCH ₃ .-CN —CN ■ greenish yellow 6th TJ JT -So ₂ - ^ y —O — C ₂ H ₄ -O- greenish yellow —O - 7th TJ —Η -CN —CN _ (*) O - greenish yellow > —O— 8th - Η —Η ■ - -CN —CN greenish yellow 9 - Η —Η -CN —CN . '.' greenish yellow 10 —Α Yy V ^CN .. - CN : i · ■ ,. '.'; greenish yellow 11th - Η -Hm: '. ·., .. . . —CN —CN - O— greenish yellow -O- -O- -O-

Example4

30 g of N-ethylaniline, 17.1 g / f,) yy ', / - diepoxytripropylamine (manufactured according to French patent 11 37 175) and 30 g of chlorobenzene are 24 hours heated to about 140 ° C., then the solvent was removed in vacuo and the residue in a high vacuum distilled. One received //, // '- Dihydroxy-yo ^ di- (N-phenyl-N-ethyl-) amino-propylamine.

Calculated ... C 72.60, H 9.51, N 10.16%; found ..;. C 72.3, H 9.7, N 10.2%.

41.3 g //, // '- dihydroxy -)',) '' - di- (N-phenyl-N-ethyl -) - amino-tripropylamine and 25 g acetic anhydride are heated to 130 "C for three hours, then ., the resulting acetic acid is removed in vacuo and the residue distilled under high vacuum to afford // // '- diacetoxy - γ, γ' - di - (N - phenyl - N - ethyl -) amino - tripropylamine: ■■ ... . <·

Calculated
found .

N 8.44%:
N 8.6%.

C 69.99, H 8.71,
C 69.6, H 8.8,

Formylicrl one this amine according to V i 1 s m c i c r and condenses the dialdehyde with malodinitrile

809 522/6

1 O \ J3 OOV

25 26

analogously to the procedure of Example 1, the bisstyryl dye of the formula is obtained

NC C ₂ II ₅ H, C,

CH = C

NC CH ₂ -CH-CH ₂ -N-CH ₂ -CH-Ch ₂

OCCH ₃ CH ₃ CO

0 O

It colors acetate, polyester and polyacrylonitrile heated, then the solvent in a vacuum

materials in greenish yellow tones. The dialde- removed and the residue distilled in a high vacuum

hyd can also be lated analogously to the examples in German. Butanediol-di- [/ S-hydroxy-y- (N-phe-

Auslegeschrift 12 06 879 can be obtained. nyl-N-ethyl-) amino-] propyl ether.

Staining instructions

1 part of the dye obtained above is dissolved in 5000 parts of water with the addition of 2 parts of 40% strength Acetic acid dissolved. 100 parts of dried polyacrylonitrile staple fiber yarn are placed in this dyebath at 60 ° one, increases the temperature to 100 ° within half an hour and colors at an hour Cooking temperature. Then the dye is rinsed well and dried. An orange color is obtained with very good fastness to light, sublimation and washing.

Example 5

30 g of N-ethylaniline, 20.2 g of butanediol diglycidyl ether and 50 g of chlorobenzene are heated to approx. 140 ° C. for 24 hours

NC

NC

Calculated ... C 70.23, H 9.07, N 6.30%;

found

C 70.0, H 8.9, N 6.3%.

44.4 g of butanediol - di - Iß - hydroxy - γ - (N - phenyl-N-ethyl) amino] propyl ether and 25 g of acetic acid hydride are heated to 130 ° C. for three hours, then the glacial acetic acid formed is removed in vacuo. Butanediol di - [/ 3-acetoxy-y- (N-phenyl-N-ethyl) - amino] propyl ether is obtained. The residue can be used directly or it can be distilled in a high vacuum. If this amine is formylated and the dialdehyde is condensed with malononitrile analogously to the procedure of Example 1, the bis-styryl dye of the formula is obtained

N N

C ₄ H ₂ -CH-CH ₂ -O- ( _{CH 2) 4} -O-CH ₂ -CH-CH ₂

OCOCH ₃ OCOCH ₃

CH = C

CN

CN

The following Table II contains a number of other valuable dyes that dye polyester fibers in greenish yellow tones and which are analogous to the regulations of Examples 4 and 5 can be obtained. The substituents and indices have the same meaning as above.

Table II Ri O
Il R ₂ O R ₃ / ■> U C ¹ JJ ptl
ν ^ Γΐ2 * - ** * - ** 2 R ₄ -QH ₄ OCCH ₃ -QH ₄ OCCH ₃ OCOCH ₃ -CH ₂ -CH-CH ₂ - -CH ₂ -CH-CH ₂ - 1 -QH ₄ OCH ₃ -QH ₄ OCH ₃ OCH ₃ OCOCH ₃ -CH ₂ -CH-CH ₂ -
I: CH ₂ CH CH ₂ 2 -QH ₃ OCONHQH ₃ ^■::: ί 'I
OCH ₃ / -> I_t CJJ CJJ '■
_{; i} 1_Γΐ2 * - ** * - * Ί2 CJJ CJJ
. · -. · .-: _ ViV ,,. ΓΗ— ₃ · ■. . : . -QH ₄ CN -QH ₄ -CN OCOCH ₃ '■ "' ■ ^lJ i ^! OCONHQH ₃ -CH ₂ CHCH ₂ - . , --- CH ₂ T-CH CH ₂ 4th C TI '- -QH ₃ - OCOCH ₃ • OCOCH ₃ -CH ₂ CHCH ₂ - 5 OCOCH ₃

l-orlset / iinii

R ₄

-CH ₃

-C ₂ H ₄ OCNHC ₂ H ₅

-C ₂ H ₄ CN

Table II (continued)

-CH ₃

-C ₂ H ₄ OCNHC ₂ H ₅

-C ₂ H ₄ CN CH ₂ CHCH ₂ -OCOCH ₃

CH ₂ CHCH ₂ -OCONHC ₂ H ₅

CH ₂ CHCH ₂ -OCOCH ₃

-CH ₂ CHCH ₂ -OCOCH ₃

-CH ₂ CHCH ₂ -

OCONHC ₂ H ₅

-CH ₂ CHCH ₂ -OCOCH ₃

Y ₁

-H

—Η

-H

2 -CH ₃ - Η CO3 3 -OCH ₃ -OCH ₃ -OCH ₃ 4th -CH ₃ ¥ T -CH ₃

—Η —CN —CN —Ν—

C ₃ H ₇

- Η —CN —CN —0— (CH ₂ J ₄ -O- -OCH ₃ —CN —CN —O— (CH ₂ ) ₄ —O—

- H —CN —CN. - N—

CH ₃

-CH ₃

-H

-H

-H

-H

-CH ₃

-H

-H

-H

-H

- H

Carb-carbethoxy ethoxy

—CN -CN

-NHCOCH ₃ -H

-NHqOCH ₃ -H-CN-CN

—CN —CN —O— (CHj) ₄ -O-

Example pi e 1-6 _; .: ■;. ■; -.

73 parts of adipic acid are converted into the adipic acid chloride _{with 168 parts of SOCl 2 , excess SOCl 2} is removed in vacuo and the acid chloride is dissolved in 250 parts by volume of benzene. A solution of 176 parts of N-ethyl-N - /? - oxyethyl-m-toluidine is added dropwise to this solution over the course of one hour and the mixture is then refluxed for 2 hours with stirring.

After: cooling, the precipitated chlorohydrate is suctioned off and washed with benzene and dried in a vacuum drying cabinet at 50 °. The product is suspended in water and the suspension is adjusted to pH 8 with sodium hydroxide solution; subsequently becomes the suspension is suctioned off and the residue is washed well with water. Remain after drying 215 parts (92%) of the product of the formula

H ₅ Q
ON

: _{M /} / C ₂ H ₄ OC- (CH ₂ ^ -COC ₂ H ₄ CH,

150 parts of this product are dissolved in 190 parts by volume of dimethylformamide and to this solution at 15 to 20 ⁰ C 109 parts by volume of phosphorous oxychloride trains dropwise with stirring, stirred for 1 hour at 95 ° and heat with stirring to 2500 parts of ice-water discharged , whereby first an emulsion is formed, from which with the

Time a greasy product precipitates, which gradually becomes completely hard. This product is in Suspended water, suctioned off and neutral with water

washed. After drying in a vacuum cabinet at 60 to 70 ", 146.2 parts (88%) of the dialdehyde are obtained the formula

/ V

CH ₃

C ₂ H ₅ H ₅ C

5 5

-NO O Ν

\ Il Il /

C ₂ H ₄ OC- (CH ₂ J ₄ - COC ₂ H ₄

Analysis: 15 drops of piperidine heated for 3 hours, then

is slowly cooled to room temperature with stirring, after 4 hours it is again 1 hour heated with stirring in a bath of 95 ° C., cooled, the resulting orange precipitate filtered off with suction and mixed with 28 parts of this dialdehyde are washed with a little isopropanol with stirring. After drying

a bath temperature of 95 ° in 300 parts by volume of iso- at 60 to 70 *, 31.4 parts (95.5%) of the color propanol remain with 7.4 parts of malononitrile and substance of the formula

Calculated ... C 58.6, H 7.7, N 5.3%;
found .... C 58.0, H 7.7, N 5.6%.

NC

NC

C = CH

C ₂ H ₄ OC- (CH ₂ ) ₄ - COC ₂ H ₄

CH = C

CH ₃

CN

CN

He dyes acetate and polyester materials in brilliant example 7

th, greenish yellow shades of excellent 35 Analogous to the procedure of Example 6, the Fastness to light and sublimation. the following dialdehyde is shown:

H ₅ C ₂ Ο

O O Ν - ^^

C ₂ H ₄ -OC CO-C ₂ H ₄ H

This compound was treated with a mixture of one molar equivalent each of malononitrile and cyanoacetate condensed in methanol with catalytic amounts of piperidine, the main product being the dye of the formula

C ₂ H ₄ OC COC ₂ H ₄

'CN ^; - ^:

CH = C

NC

COOC ₂ H ₅

was obtained as olive powder. He also dyes acetate and polyester materials in greenish yellow Nuances of excellent fastness properties. The following Table III includes a number of hamlets valuable bis-styryl dyes that have been obtained by esterification of 2 mol of the listed in column II

led N- / if-oxyethyl-amines with 1 mol of the dicarboxylic acid chlorides listed in column III.Formylation according to V i 1 smeier and condensation of the dialdehydes with 2 mol of a compound NC-CH ₂ -Y (where Yi = Y ₂ ), analogous to the Production instructions given in Example 6.

31

Table III

32

Y ίΥ, = Y ₂ )

colour

1 N-ethyl-N - ^ - hydroxy-
ethyl aniline Amber acid dichloride 2 N-butyl-N - ^ - hydroxy-
ethyl aniline Terephthalic acid dichloride 3 J
N-ethyl-N - ^ - hydroxy-
ethyl-3-methyl-aniline Terephthalic acid dichloride 4th N-ethyl-N-ß-hydroxy-
ethyl aniline Phthalic acid dichloride 5 N-ethyl-N - ^ - hydroxy-
ethyl aniline Phthalic acid dichloride 6th N-ethyl-N - ^ - hydroxy-
ethyl-3-methylaniline Oxalyl chloride 7th N-ethyl-N - ^ - hydroxy-
ethyl 3-methylaniline Cyclohexane-1,2-dicarbon-
acid dichloride 8th N-ethyl-N - / ^ - hydroxy-
ethyl-3-methylaniline Maleic acid dichloride 9 N-ethyl-N - ^ - hydroxy-
ethyl-3-methylaniline Isophthalic acid dichloride 10 N-ethyl-N - ^ - hydroxy-
ethyl-3-methylaniline 1,2,5,6-tetrahydrophthalic acid
dichloride 11th N-ethyl-B, - / ^ - hydroxy-
ethyl-3-methylaniline Glutaric acid dichloride 12th N-methy] -N- / i-hydroxy-
ethyl 3-chloro-aniline Diglycolic acid dichloride 13th N-ethyl-N - ^ - hydroxy-
ethyl-3-methyl-aniline Thiophene ^ S-dicarboxylic acid
dichloride 14th N-ethyl-N '/ mydroxy-
ethyl aniline Thiophene-2,5-dicarboxylic acid
dichloride 15th N - ^ - cyanoethyl-N - ^ - hy-
hydroxyethyl aniline Thiophene ^ S-dicarboxylic acid
dichloride 16 N-ethyl-N - ^ - hydroxy-
ethyl-3-methyl-aniline Thiophene-2,5-dicarboxylic acid
dichloride 17th N - ^ - cyanoethyl-N-fi-hy-
hydroxyethyl aniline Thiophene-2,5-dicarboxylic acid
dichloride 18th N-Ethyl-N-yZ-hydroxy-
ethyl aniline Thiophene-2,5-dicarboxylic acid
dichloride 19th N-ethyl-N - ^ - hydroxy-
ethyl aniline Ir Thiophene ^ S-dicarboxylic acid
dichloride 20th N-Ethy] -N - // - hydroxy-
ethyl aniline Thiophene-2,5-dicarboxylic acid
dichloride ί 21 N-ethyl-N-zi-hydroxy-
^ ethyl-aniline; _:>;:■;;;:.;_; Thiophen ^ S-dicarboxylic acid
: dichloride rr'i 22; - ^ - ■■■ '' _{: <} N-ethyl-NZ ^ hydroxyr ,. ".. ■ - ■
■. ' λ äthyl-anilirii rt _? :; ^; o: ■ ■■■. ■■ -; ■
.. ■ '- ■ ! -: ■ · .- .w ;. ^1. ": ■ :: ■ : ;; - · ■ .-. ;; ■." ■■: Pyridine-2,5 _: -dicarboxylic acid-
_; dichloride -T ^

23 N-ethyl-N - // - hydrpxy-

ethyl-3-methyl-aniline

COCl

CN greenish yellow CN greenish yellow CN greenish yellow CN greenish yellow COOC ₂ H ₅ greenish yellow CN greenish yellow cn '■'; · ■ ';;. greenish yellow CONH ₂ greenish yellow CN - ■;: ■■ greenish yellow CN greenish yellow so ₂ ^ 2 ^ greenish yellow CN greenish yellow CN greenish yellow cn; '■;",;' ^: - ¹ greenish yellow greenish yellow CN greenish yellow CN. : . greenish yellow _CN ■. · :, x:, iJ greenish yellow COOC ₂ H ₅ greenish yellow greenish yellow CONH ₂ greenish yellow CN giünstichiggclb CN greenish gclb

809 522/6

continuation II 15 69 699 III O COCl 34 colour 33 5-NitiO-isophthalic acid
dichloride N-p'-cyanoethyl-N-p'-hy-
hydroxyethyl aniline 5-nitro-isophthalic acid
dichloride . Y (Y, = Y ₂ ) greenish yellow 24 N-ethyl-N - ^ - hydroxy-
ethyl-3-methyl-aniline - CN greenish yellow 25th ■ N-yi-cyanoethyl-N-p'-hy-
hydroxyethyl aniline greenish yellow 26th Example 8 - CN - CN Example 9

One with the one in Example 1 (table undescribed Dye-identical dye could also be prepared in the following way: 4.82 parts (0.02 mol) of the dye of the formula

NC C ₂ H ₅

C = CH- / ~~ V-N

NC C ₂ H ₄ OH

were in 20 parts by volume of benzene with stirring with a solution of 1.1 parts by volume of succinic acid dichloride slowly added in 10 parts by volume of benzene and then refluxed for 1 hour with stirring heated and discharged on ice-water; it was extracted with chloroform, and the chloroform phase was extracted with 10% soda solution and then with 2N hydrochloric acid, with water washed neutral, dried with sodium sulfate and evaporated. The remaining oil was dissolved in methanol / ethyl acetate hot dissolved. After a while, 3 parts of the dye that was already in the example crystallize 1 Table III was described as an orange product.

30 ml of phosgene are placed in a 750 ml sulfonation flask, 100 ml of dry chlorobenzene are added and, at a temperature of -30 to -70 ° C., 1/10 mol of N-10-hydroxyethyl-N-zS-cyanathyl-aniline in 50 ml dry chlorobenzene added. It is rinsed with 50 ml of chlorobenzene, allowed to warm to room temperature, and then slowly heated to 80 to 85 ° C. and phosgene passed through until a clear solution has formed. The excess phosgene is then removed with nitrogen, 1/10 mol of N-ethyl-N - ^ - hydroxyethyl-l ^ -toluidine is added to the solution and the mixture is refluxed for three days with stirring. After cooling, the solution is extracted by shaking with dilute hydrochloric acid, washed neutral, dried and the solvent is removed in vacuo. After standing for a long time, the product begins to crystallize, is then triturated well with cold ether, filtered and dried ^{at 40 ° C. in vacuo.} The product of the following formula is obtained

Analysis:

Calculated ...
found ....

NC

NC

C ₂ H ₄ -CN H ₅ C

CH ₃

C 68.1, H 5.7, N 14.9%;
C 67.8, H 5.7, N 14.7%.

This product is formylated according to V i 1 s m e i e r and if the dialdehyde is condensed with malodinitrile analogously to the procedure of Example 6, one obtains the dye of the following formula as an olive powder

= CH

-N

C ₂ H ₄ CN

C ₂ H ₄ -OCOC ₂ H ₄ O

CH = C

CN

CN

10

example

To 100 parts of phosgene with saturated chlorobenzene 19 parts of N at 0 ⁰ C - ^ - Oxyathyl-N-zi-cyanomethyl-aniline in 100 parts of chlorobenzene was added dropwise. The mixture is stirred for 3 hours at this temperature with constant introduction of phosgene. The mixture is then heated to about 50 to 55.degree. C., stirred for about 30 minutes at this temperature and then heated to 80 to 85.degree. At this temperature, phosgene is passed in with stirring until a clear solution has formed. The excess phosgene is then blown out with nitrogen and the hot solution is filtered. This solution is added to 19 parts of N- / 3-oxyethyl-N- / S-cyanoethyl-aniline and refluxed with stirring for 24 hours. The solvent is then completely removed in vacuo, and 10 ml of ethanol are added to the residue. After two to three days, most of the residue has solidified. After filtering off, the residue becomes

Mix with cold ethanol and filter off again. After recrystallization, a product is obtained the formula

C ₂ H ₄ -CN

NC-H ₄ C,

Analysis:
Calculated
found .

C ₂ H ₄ -OCOC ₂ H ₄
O

C 67.96, H 6.45, N 13.79%;
C 68.21, H 6.37, N 13.56%.

4.1 parts of this product are at 15 to 20 ° C into a mixture of 9.2 parts by volume of dimethylformamide and 14.2 parts by volume of phosphorus oxychloride added with stirring and then 6 hours at The mixture was stirred at 60 ° C., poured onto ice, chloroform was added and the mixture was neutralized with sodium hydroxide solution. The chloroform phase is washed out with saline solution, dried with sodium sulfate and concentrated, 4.7 parts of the dialdehyde remaining as an oil. This is dissolved in hot methanol, then 1.4 parts of malodinitrile and 0.1 parts by volume of piperidine are added and refluxed for 4 hours. The dye of the formula falls on cooling

NC

NC

C ₂ H ₄ CN

NCH,

C = CH

CH = C

C ₂ H ₄ -OCO-QH ₄ O

CN

CN

as an oil, which solidifies after a while. It is ground in a mortar with a little methanol, filtered off with suction and washed with petroleum ether. After drying at 70 ^° C., 3.2 parts of a brown-yellow powder remain.

Example 11

36 parts of N-ethyl-N - (/ S-oxyethyl) -m-toluidine are mixed with 12.5 parts of diethyl carbonate and 0.2 parts Carbonic acid diethyl ester and 0.2 parts of sodium slowly heated to 170 ° with stirring in an oil bath, whereby Distilled off ethanol. After some time it is allowed to cool, the residue is taken up in benzene and shakes out with water. The benzene phase is dried, the benzene evaporated and the crude product distilled. 18.2 parts of a light yellow oil with a boiling point of 195 ° to 205 ° C. at 0.02 torr are obtained, which the formula

GH ₄ -OCOC ₂ H ₄

Has.
Analysis:

Calculated ... C 71.8, H 8.4, N 7.3%;
> found .... C 72.3, H 8.4, N 7.2%.

7.7 parts of this Kohlensäureesters be made at 15 to 2O ⁰ C with stirring in a Vilsmeier mixture

18.6 parts by volume of dimethylformamide and 28.6 parts by volume Phosphorus oxychloride entered and then stirred for 5 hours at 60 °, poured onto ice-water, adjusted to pH 7 with sodium hydroxide solution, taken up in chloroform, chloroform phase washed with saline solution, dried with sodium sulfate, concentrated. There remain 8 parts of the dialdehyde of the formula

C ₂ H ₄ -OCO-QH ₄

21 parts of the dialdehyde are refluxed for 4 hours in 300 parts by volume of methanol with 7 parts of malodinitrile and 0.5 parts of piperidine, an orange crystalline precipitate soon forming. After cooling to room temperature, the product of the formula "■ '■' ■ " · .- "■"; ■■■ '■ - j · ό; - ■'

NC

C = CH

NCi '

CH ₃

H ₅ Q

CN

QH ₅

-N N-

QH ₄ OCOC ₂ H ₄

Sucked off and washed with alcohol. After drying, 17.4 parts of the dye remain. He colors

37 38

Acetate and polyester materials in pure greenish yellow tones with excellent fastness properties and good build-up capacity.

Analysis:

Calculated ... C 69.4, H 6.0, N 15.7%;
found .... C 69.1, H 6.0, N 15.5%.

Example 12

50 parts of N-ethyl-N - (/ i-oxyethyl) aniline and 26 parts of colorless crystals with a melting point of 108 to 115 ″. After one-

Toluylene-2,4-diisocyanate are recrystallized from methanol in 50 parts of dry io times, the melting point is.

nem benzene heated in the bath at 90 to 95 °. When falling at 113 to 116''C.

cool, 73.3 parts of the crude product crystallize as The product has the formula

/ V_ _N

C ₂ H ₅ O
Il NH- -NH CH ₃ O
H H ₅ C ₂ Il
-c- \ Il \
N C ₂ H ₄ -O- Ο —C ₂ H ₄ A.

Analysis:

Calculated ... C 69.0, H 7.2, N 11.1%;
found .... C 69.1, H 6.9, N 11.5%.

10 parts of this diurethane are formylated with a mixture of 18.6 parts by volume of dimethylformamide and 28.6 parts by volume of POCl ₃ . The dialdehyde of the formula is obtained

OC ₂ H ₅ H ₅ C ₂ O

C- < VN OO N- <VC

HC ₂ H ₄ OCNh-IV-NHCOC ₂ H ₄ H

CH ₃

2.8 parts of this dialdehyde are 1en in 50 parts by volume of ethanol with 0.7 parts of malononitrile and 0.1 part Piperidine heated under reflux for 4 hours. The dye of the formula falls on cooling

NC C ₂ H ₅ H ₅ C ₂ CN

= CH- / V-NO O Ν- <f V-CH = C

NC C ₂ H ₄ OCNH-IjX-NHCOC ₂ H ₄ CN

CH ₃

as oil, which solidifies over time. It is rubbed in the mortar with ethanol, suctioned off and with Washed petroleum ether. After drying at 60'C, 1.5 parts of an orange powder remain.

Example 13

If 54 parts of N-ethyl-N - (/? - oxyäthyI) - 55 are used, 46 parts of a crude product are added after cooling

m-toluidine, 25 parts of hexamethylene-1,6-diisocyanate and melting point 58 to 60 °. After recrystallizing once

If 50 parts of benzene are used and the procedure is as in Example 12, the melting point is 60 to 62 'in methanol. The product has

if 80 parts of ethyl alcohol are added, the formula is maintained; ,

H ₅ C ₂

r ^y , - .. ■ · Il Il /

₍ '. _H C ₂ H ₄ ■ - · () · ■■■■ (' - NH (CH ₂ ) ,, - NH-C-C) -C ₂ H ₄

Analysis:

Calculated ... C 68.4, H 8.8, N 10.6%:
found C 68.4. 118.6. N 10.5%.

39

10.4 parts of this diurethane are formulated with a mixture of 18.6% by volume of dimethylformamide and 28.6 parts by volume of phosphorus oxychloride and proceeding as indicated in Example 12, 11 parts of the are obtained Dialdchyd's formula

CH,

C ₂ H ₅ H ₅ C _;

N O ON

C ₂ H ₄ OCN H (CH ₂ ^ NHCOC ₂ H ₄

CH ₃

as a light brown semi-solid crystal mass. 0.15 part of piperidine heated under reflux for 5 hours

5.8 parts of this product are in 60 parts by volume and this solution is then made up with stirring

absolute alcohol and 30 parts by volume of dimethyl 1000 parts of water discharged, acidified and that

formamide with 1.4 parts of malononitrile and ι j precipitated brown-orange product of the formula

NC

NC

C = CH

CH ₅ H ₅ Q

NO ON

\ Il Il /

C ₂ H ₄ OCNH (CH ₂ ) ₆ NHCOC ₂ H ₄

CH = C

CN

CN

suctioned off and washed with water. After drying, 4 parts of the dye remain.

The following Table IV includes a number of other valuable bis-styryl dyes which are produced by condensation of 2 moles of the N- / V-oxyethyl-amines listed in column II with 1 mole of the in column III listed bis-isocyanates, formylation according to ViIs-

Table IV

Meier and condensation of the dialdehydes with a compound CN ■ —CH ₂ —X, analogously to the instructions of Example 13 can be obtained. The dyes dye acetate and especially polyester materials in greenish yellow tones with excellent fastness properties. I.

III

colour

1 N-ethyl-N-hydroxyethyl-3-methyl-aniline

2 N-ethyl-N-hydroxyethyl-3-methyl-aniline

3 N-ethyl-N-hydroxyethyl aniline

4 N-methyl-N - ^ - hydroxyethyl aniline

5 N-methyl-N '/ Z-hydroxyethyl aniline

6 N-methyl-N-hydroxyethyl aniline

7 N-ethyl-N-zi-hydroxyethyl aniline

8 N- / i-hydroxyethyl

1,2,3,4-tetrahydroquinoline

9 N-ethyl-N / Z-hydroxyethyl aniline

K) N-ethyl-N-z-hydroxyethyl-3-methyl-aniline

11 N-ethyl-N-zZ-hydroxyethyl-3-methyl-aniline

12 N-ethyl-N-zi-hydroxyethyl-3-chloro-aniline

Toluene-2,4-diisocyanate - CN yellowish 809 522/6 green Toluene-2,4-diisocyanate -COOC ₂ H ₅ yellowish green Hexane-1,6-diisocyanate —CN yellowish green Hexane-1,6-diisocyanate —CN yellowish green Phenylcn-1,4-diisocyanate - CN yellowish green Phenylcn-1,4-diisocyanate -COOC ₂ H ₅ yellowish green Phenylene-M-diisocyanal —CN yellowish green Phenylene 1,4-diisocyanate - CN yellowish green OCN - <^ \ - CH ₂ - / \ --NCO - CN yellowish ■■ '" green OCN - <f V-CH ₂ - ^ \ -NCO - ■ CN yellowish green ocn - ^ S v \\ ₂ - <f \ Nco COOC ₂ H ₅ yellowish green OCN <^ \ CH ₂ / ^> NCO CN yellowish green

41 42

B e i s ρ i e 1 14

In 35.8 parts of N-ethyl-N-zy-oxyäthyl-m-toluidinwer- with methanol being distilled off. The residue with

dissolved with heating 0.2 parts of sodium, then distilled under high vacuum. You get the pros

41.4 parts of N-ethyl-N - ^ - carbomethoxyaniline added dukl of the formula y

ben and slowly heated to 250 C while stirring,

! O N

\ Il /

C ₂ H ₄ COC ₂ H ₄

as a colorless oil, bp 185 to 195. This amine is formylated according to Vi 1 m e i r and

i) analogously condenses the dialdehyde with malonitrile

Analysis: following the rules of example 6, one obtains the

Calculated ... C 74.5, H 8.5%; Dye of the formula

found .... C 74.4, H 8.3%.

NC C ₂ H ₅ H ₅ C,. CN

O N- / V-CH = C

NC C ₂ H ₄ -COC ₂ H ₄ Vu ^CN

which acetate and polyester materials in greenish yellow tones with very good fastness properties colors. .

Claims (3)

by Claims: Water-insoluble styryl dyes of the formula NC R ₁ R ₂ = CH-A ₁ -N-Rj-ZR ₄ -NA ₂ -CH = Y ₁ wherein Ai and A _{2 are} unsubstituted or substituted by lower alkyl, lower alkoxy, halogen; Phenoxy, thiophenoxy, trifluoromethyl, acetylamino or aminocarbonyl substituted p-phenylene groups, R ₁ and R ₂ hydrogen, alkyl with one to four carbon atoms, with halogen, hydroxy, methoxy, ethoxy, cyano, phenyl, acetoxy, cyanoethoxy, cyanoacetoxy, benzoyloxy as substituents , Methylcarbamoyl, phenylcarbamoyl in question, and /; - Carbo (methoxy, ethoxy or propoxy) ethyl (where the terminal alkyl group in the (»'position can carry cyano or an amino group), [! - or γ-carbo- (methoxy or ethoxy) propyl, / i-acetyl or formyl) aminoethyl, // - acetoxyethyl, //, y-diacetoxypropyl, / v'-methanesulfonylethyl, // - ethanesulfonylethyl, / Hp-chlorobenzenesulfonylethyl, / / -Methylcarbamyloxyäthyl, // - Phenylcarbamyloxyäthyl, / HMethoxy-, ethoxy- or -isopropyloxy) -carbonyloxyäthyl, γ-Acetamidopropyl, // - (p-Nitrophenoxy) -äthyl, // - (p-Hydroxyphenoxy) -äthyl, / H / j'-AcetyiäthoxycarbonylJ-ethyl, / ('- [// - (cyano-, hydroxy-, methoxy- or acetoxy) ethoxycarbonyl] -ethyl, / ί-carboxyethyl, γ-amine opropyl, /; - diethylaminoethyl, / f-cyanoacetoxyethyl, benzoyloxyethyl and p-alkoxy- or phenoxybenzoyloxyethyl; or with A ₁ or A ₂ 2,2, 4,7-tetramethyl-l, 2,3,4-tetrahydroquinoline, 7-methyl-l, 2,3,4-tetrahydroquinoline or 1,2,3,4- Form tetrahydroquinoline; R ₃ and R ₄ alkylene groups with up to. 4 carbon atoms which can be substituted by hydroxy, acetoxy or ethylcarbamyloxy mean, Z is - O—, —S— —NH- C ₁ -C ₃ alkyl
NH-CH ₂ CH ₂ -NH- XT 4 ") 50 CN Y ₂ R ₅ for branched or chain-like aliphatic divalent hydrocarbon radicals with 2 to K) ■ carbon atoms, radicals of the formulas - CH ₂ CH ₂ -O-CH ₂ CH ₂ -. .
- CH ₂ CH ₂ - O - CH ₂ CH ₂ - O - CH ₂ CH ₂ - the phenylaraliphatic hydrocarbon radicals with 7 to 15 carbon atoms mentioned in the description, phenylene-aromatic hydrocarbon radicals having 6 to 15 carbon atoms, and cyclohexylene, Z is also the divalent Remnants of the formulas —C —O— ι Μ —O — c— Il O
CO — NH-CO- NH- CO- "'"
CO-NH
CO-NH-CO- ^
O- ^ CO — CO — Ο—
CO-NH-NH-CO
4NH-CO-GO-NH Xi ν V ' -N-CH ₂ CH ₂ -N-CH ₃ CH ₃ 55 60 —O — CH ₂ CH ₂ —NH — CH ₂ CH ₂ —O— or the radical of the formula —O — R ₅ - ^ O-, in which denotes where X '= - O - or imino and Z' is the acyl radical an organic dicarboxylic acid having 2 to 16 carbon atoms, an organic dicarbamic acid having up to 15 carbon atoms, a radical of the formula - OCO-X '- R ₆ -X'- OCO- is, where R ₍ , is an aliphatic or phenylene aromatic radical with 2 to 10 carbon atoms; or, if R ₃ and R ₄ stand by opening of oxirane rings, optionally by aliphatic see carboxylic acids with up to 3 carbon atoms or ethyl or phenylcarbamic acid esterified Ν, / j-hydroxy-ethylene or -propylene groups, an aliphatic or phenylaromatic residue with up to 15 carbon atoms, which is optionally bonded on both sides via —Ό— and Y ₁ and Y _{2 are} cyano, dC 1-4 alkoxycarbonyl or phenylsulfonyl groups. 2. Bisstyryl dyes according to claim 1, wherein Z 'is the diacyl radical of an aliphatic. Dicarboxylic acid with 3 to 16 carbon atoms, a cyclohexanedicarboxylic acid, a phenylene aromatic dicarboxylic acid having 8 to 16 carbon atoms or a thiophene or pyridinedicarboxylic acid. 3. Use of the dyes according to Claims 1 and 2 as disperse dyes for dyeing of fibers containing ester groups, of polyacrylic fibers or for pigmenting high molecular weight organic material.