DE1569699C3 - 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

-N-CH ₂ CH ₂ -N-

CH ₃
- Ο — CH ₂ CH ₂ ¹

CH ₃

¹ CH ₂ CH ₂ -O

or the rest; of the formula - O - Rs - Q -, where R _{5 is} . branched or chain-like: aliphatic divalent hydrocarbon radicals with 2 to 10 Kph-25 atoms, radicals of the formulas. . ,

The present application relates to new, valuable, - CH ₂ CH ₂ - O -CHiCH ₂ - O. - CH ₂ CH ₂ -

water-insoluble styryl dyes of the formula; V 30 '

the phenyiaraliphatic hydrocarbon radicals mentioned in the description with 7 to 15 carbon

NC Ri- R ₂ / CN atoms, phenyl aromatic hydrocarbon

\ I I / residues with 6 to 15 carbon atoms, and cyclo-

C = CH-A ₁ -NR ₃ -ZR ₄ -NA ₂ -CH = C 35 hexylene, Z also represents the divalent radicals of

/ \ Formulas

^ ■ —c — o— —o — c— —o — c — o—

wherein A ₁ and A _{2 are} unsubstituted or by lower 40 II II II

Alkyl, lower alkoxy, halogen, phenoxy, thio, O OO

phenoxy-frifluprmethyl, acetylamino or amino- - qq —NH — CO— -NH — CO—

carbonyl substituted p-phenyl groups; R ₁ ^ and R ₂ "_ _ _r ._ _nr ._ _rn _ _n __

Hydrogen, optionally substituted alkyl with one _f to four ^{C (J NM} - ^! ' ^{: M 1} ^ ^ ^υ ■

Carbon atoms, where the substituents are Hajogen, 45 -CO-NH-NH-GO _; ; ; .-

Hydroxy, methoxy, ethoxy, cyano, phenyl, acetoxy,. _; . - "., '·>,,.,.

Cyanoethoxy, cyanoacetoxy, beiizoyloxy ,. Ethylcarb- NH CO CO-NH--:,.: amoyl, phenylcarbamoyl are possible; as.

/; - Carbo (methoxy-, ethoxy- or prbpoxy) äthy! (\ Ypbe: i. ^Or ν

the terminal alkyl group in the ^ / - position Cyano pid'er 50 χ> . £ '—χ'—

an amino group trägeir kaiin), /A-,pder^'y.-Carbp- ;; y- .'..--. j-i- < _. · - ■■ _>

(methoxy-i 'or ethoxy) propyl, // - (acetyl- "or Fpr-

myI) -amiripätnyr ^ ^{: i} /) '- Acetbxyäthyl,' ^, y-Diacetpxy'prpr. means where X '= - O or imino and Z' is the

pyl, ^ -Methanesulfohyläthyl-, '// - Äthansuifonyläthyl,' acyl radical of an organic dicarboxylic acid with 3 to

// Hp-ChlorbehzolsulfPnyliäthyi; '' '/ i-Metnylcarbamyl- .; 55 16 carbon atoms, an organic dicarbamiri- '

oxyäthyi, ^ -PhenylcarbämyloxyäthyK // - (Methöxy- / acid with up to 15 carbon atoms, a remainder of the

ethoxy-ödei-isppröpylöxyj-cafbphylöxyä Formula - OCO - X '---R ₆ - X' - OCO - is what-

amidopröpyl, '^^ - Nitrppheno ^^ in R ₆ an aliphatic, or phenylene aromatic

drbxypHenokyj-äthyl, '"', ^ - (^ ' ^: AcetyiätHbxycarbenpnyl) ^ i is a radical with 2 to 10 carbon atoms; or, when R ₃

äthyl, Ii- (Ji '- (Cyaiio-l Hydfpxy- ^ Methbxyr.pder ^ AcetT' 60 and R ₄ resulting from the opening of oxirane rings,

oxy) -äthÖxycarbonyl] -äthyl,, // - Carboxyäthyi, y-Ami- optionally with aliphatic carboxylic acids

_nbprbpyl: ^ piäthylärninpäthyl, ^ -C ^ anacetpxyäthyk: up to 3 C-Atpmen: pder ethyl or Phenylcarbamin-

Benzylpxyäthyrund p-Älkpxy- or Phenpxybenzpyi- ^ acid esterified 'N ^ -hydroxy-ethylene- or -pro-

mean oxyäthyl; "or with A ₁ or _: Ä2 2 ^ 2,4,7! -f etra-: pylene groups; are, ^ an aliphatic or phenyl-

methyl -. '1,2,3,4- tetrahydrochplin, 7 r methyl - 1,2 ,! 65 aromatic radical "with up to 15 carbon atoms,

3,4-tetrahydrbchiripiin or: 1,2,3,4-fetrahydroquino- der optionally bonded on both sides via - O -

form lin; R ₃ ¹ and R ₄ alkylene groups with up to "; 4 is Koh- ] and Y ₁ and Y _2: cyano, C _: C ₄ -alkoxycarbonyl- or .:

lenstoffatörnen, which are through hydroxy, acetoxy or phenylsulfonyl groups.;, ._:.,.; -,; /. ··,

The new dyes can be obtained / .. B. if one either

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 = 1, Y 1 ′ and Y ₂ ′ together with Z form an addition-friendly 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 from one another so that one leads to asymmetrical styryl dyes)! got.

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

O-

where X, and X _{2 represent} a group containing at least one reactive hydrogen sulfide, preferably an amino, mercapto or hydroxyl group, or their reactive derivatives and R ₁ , R ₂ , R3 and R _{4 are} optionally substituted alkyl or alkylene groups UHdA ₁₅ A ₂₅ Yi and Y _{2 have} the same meaning as above, _{or reacts with a bifunctional compound free of SO 2} groups to give the dyes of the formula (1) according to the invention

b) the dialdehyde of the formula

R ₁ R ₂

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

Y ₁

C = CH-A ₁ -NH-R ₁

NC

Y ^ -

with a bifunctional compound of the formula

"■ '■ Yi ~~ (Rl) i> 1 Ζ— (R ₄ J ₁ TTy ¹ ; Y2 ϊ;' / -

converts, where /; an integer in the value vein 1 or 2 and Y, 'and Y ₂ ', when / is 1-2, each a reactive negative radical, preferably a haloalom. is

called, where C ₁ , C ₂ , d! and d 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 melhoxy 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 alkylsulfonyl group, preferably a methylsulfonyl 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 monoamide, such as phenoxycarbpnyl, methoxycarbonyl and aminocarbonyl. ^; . λ

The groups d! and d ₂ are preferably bonded in the ortho position to the coupling-directing amino group. . " _: 'Λ j'." _ "., I .:, ..;, '. / <, .- ..

pie.Gruppeh Ri and R ₂ könrieri hydrogen atoms, or ^{Alkylgrupperi:} substituted alkyl groups. bcr indicate ^ ie ^ Chlorälhyl-V / ^ / ÄTriflüoräthyl-, fi, yD} - ', ^{chloropropyl,',:} / i: Cyanäthy | - ,. ;; ' / ^ Äthpxyäthyl- or . j'-Methdxybutyl.- ,, y / -Hydroxyethyl-, '' 7 ('»5':. P ^l 'riyf! ^r 9 ³ ' ypropyU, / y-nitroethyl, // - Carbofrhelhöxy-, ethoxy- or propoxy) ethyl (where the terminal alkyl group iri '(- i'; position cyano, carbalkoxy - ";" acyloxy-, and Ariiinpgrüpperi can carry, / fl or ^ -Carbo- (methoxy- or ethpxy) -propyl-, / . / - (acetyl barren research, 'mylj-amihö-ethyl - ^, ^' // - AcetylOxyäthyl - '^ // - / - piacctoxypropyl-, vi Methansulipnyläthyl-l; y ^ ^{Äthansulfohyläthyl-,! 1} or // - (pfChlorbcnzplsulfpnylHäthyl-, '-' / »'- Mc-'. 'Thylcarbarnylpxyäthyl-, ^ '' and |' * // ^: Phcnyicarbamy | pxyäthyl-, ¹ // - (Mcthpxy-; ethoxy- odor '-is () prbpyioxy) -iiar-' ^{bonylöxyäthyl:,} y-Acetarnidopropyl- // - (ρ-Nitrophcri oxyi-diethyl - ^ '/ RTP Hydroxyphcnoxyl-ethyl; // - (//' - Acetyläthöxycarbonylj -äthyl-, // - [/ '''- (cyano-, hydroxy-, methoxy- or acctoxyj-alhoxycarbonyn-ethyl-. cy-

analkoxyalkyl-, / <- C.arhoxyälhjl-. , < - Acelyläthyl-. ; -Aminopropyl-, / i-Diälhylaminoälhyl-. / i-Cyanaceloxyäthyl- and /i-Benzoyl-/j-(p-Alko.\y- or Phenoxvbcnzoyl-oxyäthyl- groups. The groups R ₁ and R ₂ generally contain at least 2 carbon atoms and not more than eight, preferably not more than six, carbon atom c.

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

H— A ₁ -N-

Η —Α, —Ν

ιο

the end. Possible are e.g. B. 2,2,4,7-tetramethyl-1,2, 3,4-letrahydroquinoline and 7-methyl-1,2,3,4-tetrahydroquinoline.

The groups R ₃ and R ₄ are optionally substituted alkylene groups preferably having at least two carbon atoms, such as. B. unsubstituted ethylene groups or, according to a particular embodiment of the invention, alkylene groups hydroxylated in / i-position to the amino group. The latter are formed for example in the _two-sided% reaction of diepoxides, in particular Diglycidylverbindiingen, with the at least one reactive hydrogen atom-bearing components

HA ₁ -NHR, and HA ₂ -NHR ₂

- O— —S—

- NH- —Ν -

or the corresponding styryl dyes !!. The hydroxyl groups formed in the / y position can be substituted, and the substituents, 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 glicd, groups of the following formulas are particularly suitable:

-NHCH ₂ CH ₂ NH
N CH ₂ CH ₂ -N
(Ή., CH.,

O CH ₂ CH ₂ NH CH ₂ CU ₂ O
() ■■ R, '<>

where Ks is one of the divalent aliphatic, arali-

phalic or aromatic residues of the formula

CHv-CHv-

CH, -

-CH

CH,
C.

CH,

and especially the groups of the acyl residues Formulas

- OCO-

- OCOCOO -

- CONH-
- CONHNHCO -

as well as the colorless link of the formula
- X'CO - R ₍₁ - COX'-

- OCOO -

- NHCO -— CONHCO—
—NHCOCONH

where 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 formula

- X '- CO - NH - R ₇ - NH - CO - X' -

where 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

V-

cu _:

is, the colorless link of the formula
- OCOX '- Rk-X' - OCO

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

ho heterocyclic radical. is. which can be interrupted by groups X 'when X- is an NH group. R _{x has} the same meaning as R- .. ^

To the. Bypassing the link Z, proceed as follows: Λ

b5 The linkage takes place via dicarboxylic acid esters according to known methods. / .. B. by esterification, especially with a / eotropic elimination of water, by transesterification with elimination of a volatile one

809 522/6

Alcohol or phenol or by reaction with dicarboxylic acid anhydride, by reaction with dicaibonic acid halides. where the tertiary amino group present on the phenylene radical A 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 diisocyanate !! to, preferably either in inert solvents or works 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 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. The carbonic acid esters can be> o however, they can also be produced by transesterification with dialkyl or diary carbonates.

When X is an amino group having at least one active hydrogen atom, it is preferably obtained the corresponding [^ carboxamides 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

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

Oxalic acid,

Succinic acid,

Malonic acid,

Pimelic acid.

Adipic acid,

Methyl adipic acid,

Azelaic acid,

Sebacic acid,

Maleic acid,

Fumaric acid,

Ally! 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,

Hexachloroendomethylene tetrahydrophthalic acid,

Phthalic acid,

Isophthalic acid,

Terephthalic acid,

2,5-thiophenedicarboxylic acid,

Furandicarboxylic acid,

the dicarboxylic acids of the formulas

COOH

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

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) urea,. · .;

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

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

Stilbene-4,4'-diisocyanate,

Benzophenone 4,4'-diisocyanate,

Diphenyl ether or diphenyl sulfide diisocyanate, as well as their substitution products, e.g. B. derivatives substituted with alkyl, alkoxyl, halogen or nitro groups, such as B. 3,3'-dimethyl- or 3,3'-dimethoxy- or IJ'-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 reacting 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.

Suitable divalent aliphatic ^, cycloaliphatic, araliphatic or aromatic hydroxyl compounds, whose hydrocarbon structure is optionally interrupted by heteroatoms. are for example the following hydroxyl compounds are listed:

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, -heptane, -octane, -nonane, -decane, -undecane, -dodecane, -hexadecane, -octadecane,

1,4-dihydroxybutene,

l, 5-dihydroxy-2,2-dimethylpentane,

Di - (/ y-hydroxy-ethyl) -thioether,

Dir (/ j-hydroxy-ethyl) -ether (= diglycol),

Triglycol,

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

4,4'-dihydroxydicyclohexylmethane,

4,4'-dihydroxydicyclohexyldimethylmethane,

4-hydroxybenzyl alcohol,

I, 4-Di - (// - hydroxy-ethoxy) -benzene,

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

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

2.5- or 3.5-) dihydroxybenzene,
1,4-Dimethyl-2,5-dihydroxybenzene,
1-ethyl-2,4-dihydroxybenzene,
l-isopropyl-2,4-dihydroxybenzene,
4,4'-dihydroxyazobenzene,

2,4- or 4,4'-dihydroxydiphenyl ether,
2,2'-dihydroxyethylene glycol diphenyl ether,

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

2,4'- or 4,4'-dihydroxydiphenyl,
4,4'-dihydroxydiphenylmethane,
4,4'-dihydroxydiphenyldimethylmethane,
1,1 '-Di - ^' - hydroxyphenylJ-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-yS-chloroethyl ether, dichloroethyl formal and the isomers of bis (chloromethyl) benzene.

If you put the dyes of the formulas

NC

NC,

C = CH-Ai-N-R ₃ -X ₁

■■■■ - ^f ■ ' ^{> y} R ₁

C = CH- ¹ A ₂ -N-R ₄ -X ₂

Thiol, carboxyl or, in particular, amino groups, with a diepoxide, are obtained as terminal Groups of the bridge member Z ethyl, thioether, ester or imido bridges, while 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 group —R ₃ —Z — R ₄ - 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 R ₂

C = CH-A ₂ -NH

or p-aminophenyl 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 / i-position to 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

wherein Xi and X ₂ each have a reactive hydroxyl, thus obtained by addition of a diepoxide to two coupling components or azo dye radicals 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: Houben-Weyl, "Methods of Organic Chemistry", Volume 14, Part 2, Stuttgart, 1963, pp. 462 to 567 has 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 may be carried out at room temperature already, but it will react at amino groups on the aromatic ring at temperatures of 30 to 150 ⁰ C.

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

with the free amine hydrogen of the group of the formula H - NR - to the / i-hydroxyamine of the formula

C — CH-NR-

OH

reacts, where R is one of the radicals R ₁ or R ₂ . The hydroxyl groups formed by the opening of the 1,2-epoxy rings can subsequently be substituted, in particular aeylated; 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 ₁ and R ₂ , which are derived from an N - ^ - hydroxyethyl group, but in particular the "residues 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.

Bisstyryl dyes that differ from a C, N-diglycidyl-alkylamine as a middle component

3 L 1x4

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

NC

C = CH-AN (R) -CH ₂ -CH (UHJ-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

and the dye of the formula

C-CH A ₂ ^ N (R ₂ I-CH ₂ -CH (OII) -CHj-X

reacts differently and before or after the fourth group R ,, with an alkylating agent R ,, - X condensed on the qualified nitrogen atom, where X is an easily split off negative residue, 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 (mercaptomethyl) benzenes, the N, N'-diglycidyl compounds, e.g. from 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

OCH-A ₁ -NR ₁ -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

R ₁

R ₂

HA ₁ -NR _-1 -ZR ₄ -NA ₂ -H

with dimethylformamide and phosphorus oxychloride according to Vilsmeyer 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 —coo— - ocoo -

OR 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, in particular h ^r > but dialdehydes in whose Z at least one acyl group belongs or by reacting 2 moles of aromatic amine with 1 mole of dicpoxide deslanworin X has the same meaning as above - that is.

16

The following dialdehydes are listed as examples:

OCH

OHC

CH., \ S CHj

~~ VN -C ₂ H ₄ - N-C ₂ H ₄ - N ^ (~ \ - CHO

\ - \ I - Γ.Η.ΠΓ.Η. — M— P \ —CHO

C ₂ H ₅ C ₂ H ₅

NC ₂ H ₄ OC ₂ H ₄ -N

C ₂ H ₅ C ₂ H ₅

^ -N- C ₂ H ₄ OC ₂ H ₄ -N ^^^^ CHO

CH, CH,

CH,

CH ₃

OHC sy ^ vK _- Jv ₁ J CH ΓΗ. ^ * '"' • J ^ ¹ - ¹ f ^ ^ ¹ J ^ U —M— ''

and the dialdehydes of the formula

OHC

^Λ 2 * - '' 2

C ₂ H ₅ O-CH ₁ -CH ₇ -O-Ch ₇ -CH ₇ -

C ₂ H ₅

/ VNC ₂ H ₄ -ZC ₂ H ₄ -N- ^ V-CHO

CH,

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

-NH- —Ν—

I.
Alkyl

-OCH ₂ CH ₂ O- -N-CH ₂ CH ₂ N-CH, CH,

-OCH ₂ - ^ "V-CH ₂ O-.

-OCO-. - OCOO- ₇ () CONHCH ₂ CH ₂ NHCOO CONHCO- -CONHNHCO

CONH - <f / NHCO

OCONH <r / ■■ NHCOO

'NIICi) CH ₂ (Ii ₂ CONII NHCO-

CH,

J X

CONH—

O-

-O CH ₂ CH,

SO-

-O-

CH,

M)

h5 OCOCOO

OC NIi H ^ -i \ y. _g ClU 4 -NH CO

O ■■ (· '■' NH (CH, ir NH C

■. ir · ^: · ■ - - "■■■■■■»

ο ο

NHCOCONH

809522 / β

17th

Furthermore, the aldehydic animal formulas

18th

CH,

OHC

OHC

-N-CH,

C ₂ H ₅ H ₅ C

I \

CLJ r \ Γ ~ * LI 2 Γ14 \ J L-2 ¹ M-

C ₂ H ₅

CH ₂ -N-f V-CHO

CHO

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

C, H

2 "5

H.

// V

CHO

Ch ₂ -CH-CH ₂ -N-CH ₂ -CH-CH ₂

OH CH OH

/ \ CH ₃ CH ₃

, C ₂ H ₅ H ₅ C ₂

OHC

N-

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 .:

CH ₅

H ₄ C
ON

CH ₃

CH ₅

CH ₄ -OCO-CH ₄

CHO

CH ₃

OHC

// V

H ₄ C
O N-? V-CHO

CH ₄ -O -C -NH- (f VNH-COC ₂ H

CH ₃

C ₂ H,

1 "5

OHC

CH ₃

0HC

H ₅ CNO ON

. \ Il Il /

^t! QH ₄ -OC-NH- (CH ₂ ) S-NH-COC ₂ H ₄

CHO

.CH,

NCH ₄ C

CH ₄ CN NO

\ Il Il /

CH ₄ -OC- (CH 2) _n -COC ₂ H ₄

O N- <V-CHO

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

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 ι ο ζ. Β. 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 a basic catalyst in glacial acetic acid or another organic acid or in the absence of a solvent by melting the reactants together in the presence of a basic catalyst, 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

R.

R ₃ ,

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

(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. * 25 83 551.

Compared to the bisstyryl dyes described in French patent specification 14 49 542, in which the dye residues _{are connected via a ^ -SO 2} bridge, the dyes according to the invention are distinguished by significantly better drawability 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 especially aromatic polyesters. Even the hydrophobic ones Fibers made from copolymers of propylene oxide and unsaturated epoxies and fibers on polyvinyl chloride basis can be colored with the new dyes.

It is obtained on hydrophobic fibers, in particular on polyester fibers, by the usual dyeing processes, for example from a dye liquor which contains a fine dispersion of the dye and advantageously a dispersant, at temperatures up to close to 100 ^° C., optionally with the addition of a swelling agent, or at temperatures above 100 ⁰ C under appli cation of excess pressure, pure, robust, grünstichiggelbe dyes, which are characterized by excellent light and sublimation. 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 so impregnated fabric, expediently after previous drying, for. B. in a warm air stream to temperatures of over 100 ° 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 block fluid 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 are used for a wide variety of purposes Pigment applications can be used, e.g. B. in finely divided form for dyeing rayon and Viscose or cellulose ethers and esters or of super polyamides or super polyurethanes or polyesters in the spinning mass, as well as for the production of colored lacquers or lacquer formers, solutions and Products made from 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.

ί Example 1 r _{; f} .>..;;.

48.8 parts of N-ethyl-N - (/ S-oxyethyl) -m _: toluidine in 30 .yoI.TTe.ilen dry benzene are stirred with 11 parts of sodium metal for 15 hours under reflux, excess sodium is removed and then 53 , 8 parts of N-ethyl-N - (/ S-chloroethyl) -m-toluidine in 50 parts by volume of dry benzene and 4 parts of sodium iodide were added. The mixture is refluxed for a long time with stirring, then diluted with dry benzene. The sodium chloride and sodium iodide formed 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

N-CH ₄ -OC ₂ H ₄ -]

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.,

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 also obtained by reacting 2,2'-dichloro-diethyl ether with N-ethylm-toluidine.

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

10

15th

C ₂ H ₅

C ₂ H ₅

VN-C ₂ H ₄ -OC ₂ H ₄ -N

CH.,

back as dark Dl.

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

C ₂ H,

C = CH

r » r · IJ κι / y χ

NC ₂ H ₄ -OC ₂ H ₄ -N

CH = C

CH,

CH ₃

CN

CN

Analysis:

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

It dyes polyester fibers in a 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 dinaphthylmethanedisulfonic acid, wet grinding and drying.

This dye preparation is mixed with 40 parts of a 10% aqueous solution of the sodium salt 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 of a cleaned polyester fiber, increases the temperature in half an hour to 120 to 130 "and stains in a closed vessel for one hour Temperature. Then it is rinsed well. A greenish yellow coloration of excellent is obtained Right to light and sublimation.

B e i s ρ i e 1 2

If the starting material used is the dialdehyde of the formula

35 C ₂ H ₅

OCH NC ₂ H ₄ -OC ₂ H ₄ -N

C ₂ H ₅

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.

B e i s ρ i e 1 3

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

C = CH

.C ₂ H ₅

CH,

C ₂ H ₄ -OC ₂ H ₄

CH ₃

COOC ₂ H ₅

This produces greenish-yellow colorations with good fastness properties on polyester materials. Table I below contains a number of other valuable dyes of the general formula

NC

Y ₁

C ₂ -: -

C CH

N- R, - ZR ₄ - - Ν-

which are obtained in a manner analogous to Example I.

Tabel

example

23

24

-CH ₃ -CH ₂

-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 ₅

C ₂ H ₅ -C ₂ H ₅

Il

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 -C ₂ H, C ₂ H ₄ OCNHC ₂ H ₅ -C ₂ H ₄ 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 -QH ₄ C ₂ H ₄ -C ₂ H ₄ CH ₂ -CH-CH ₂ - 0
Il C ₂ H ₄ Il
OCCH ₃ -C ₂ H ₄ 1

-CH ₃
-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 CH3 - Η Y ₁ Y ₂ Z ? " ³ _ ■ '"■■ —Ο— colour game - Η - Η —0— j 1 -CH ₃ —Η -CN -CN —Ο— CH ₃ ,, .— Ο—-. .. ■. _v rr. greenish yellow 2 -CH ₃ —Η -CN -CN .-'- ■ - Ο— greenish yellow 3 -H -OCH ₃ -CN -CN —Ο — C ₂ H ₄ -O- greenish yellow 4th - Η - Η -CONH ₂ -CONH ₂ —Ο— greenish yellow 5 . -CN -CN greenish yellow 6th —Η - Η -SO ₂ - ^^ -SO ₂ - ^) —Ο— greenish yellow 7th - Η —Η -CN -CN greenish yellow - Η - Η 8th -Cl IJ .-: -—CN: -CN greenish yellow 9 - Η -Hm -CN -CN greenish yellow 10 -CN, -CN ; \ greenish yellow 11th ..: - CN "■ - -CN greenish yellow

Example4

30 g of N-ethylaniline, 17.1 g / ^, // ', / - diepoxylripropylamine (manufactured according to French patent 11 37 175) and 30 g of chlorobenzene are -24 hours to ca; 140 C heated, then the solvent removed in vacuo and the residue distilled in a high vacuum. / F, // '- pihydroxy -)', / - di- (N-pheriyl-N-ethyl-) amino-tripropyJamine were obtained.

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

41.3 g //, / r-Dihydroxy-yy-di-CN-phenyl-N-ethyl -) - amino-tripropylamine and 25 g acetic anhydride are heated to 130 "C for three hours, then the glacial acetic acid formed is removed in vacuo and the residue is distilled in a high vacuum. This gave //, // '- diacetoxy - γ, γ' - di - (N - phenyl - N - ethyl -) amino - tripropylamine: "

Calculated ... C 69.99, H 8.71, N 8.44%;
found .... C 69.6, H 8.8, N 8.6%.

This amine is formulated according to V i 1 s m c i e r and condenses the dialdehyde with malodinitrile

809 522/6

25 26

analogously to the procedure of example 1. the bisstyryl dye of the formula is obtained

NC CMI ₅ H, C ₂

C = CH - <^> - NC ₃ H ₇ N - <^ 3 ^ CH = C

NC CH ₂ -CH-CH ₂ -N-CH ₂ -CH-Ch ₂ CN

OCCH ₃ CH ₃ CO

O 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- [/? - 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 within half an hour to 100 ° and colors one hour at 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. C ₂ H ₅

C = CH - ^ ~ \ -N

Calculated ... C 70.23, H 9.07, N 6.30%;
found .... C 70.0, H 8.9, N 6.3%.

44.4 g butanediol - di - {ß - hydroxy -γ- (N-phenyl-N-ethyl) amino] propyl ether and 25 g of acetic hydride are heated for three hours at 130 ⁰ C, then the resulting glacial acetic acid 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

CH = C

NC

QH ₂ -CH-CH ₂ -O- (CH ₂ ) ₄ -O-CH ₂ -CH-CH ₂ OCOCH ₃ OCOCH ₃

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

Il

Il

-C ₂ H ₄ OCCH ₃ -QH ₄ OCCH ₃ -CH ₂ -CH-CH ₂ - CH2 CH CH2 OCOCH ₃ OCOCH ₃ -QH ₄ OCH ₃ -QH ₄ OCH ₃ -CH ₂ -CH-CH ₂ - -CH ₂ -CH-CH ₂ -
. ■ ■ I OCH ₃ OCH ₃ -QH ₃ 1: - '.' // T: -QH ₅ '—CH ₂ -CH-CH ₂ -
■ - .. · 'I ■ ■' ■. .....-- CH ₂ -CH-. : ;: ■■■ '-' ■ ·: · - '■' ■ ' OCONHC ₂ H ₅ '} \' ^: - OCONHC ₂ H ₅ -QH ₄ CN -QH ₄ -CN .., .— CH ₂ CH CH ₂ - ^; OCOCH ₃ :, _; OCOCH ₃ -QH ₅ - -QH ₅ - ² 1 ² -CH ₂ CHCH ₂ -
I. OCOCH ₃ OCOCH ₃

R ₁ O
Il 27 15 69 R ₂ O 699
28 R ₄ -CH ₃ -CH ₃ -C ₂ H ₄ OCNHC ₂ H ₅ -CH ₂ CHCH ₂ - continuation OCOCH ₃ C HjC H C H 2 -CH ₂ CHCH ₂ - 6th OCOCH ₃ OCONHC ₂ H ₅ -C ₂ H ₄ OCNHC ₂ H ₅ -CH ₂ CHCH ₂ - -CH ₂ CHCH ₂ - 7th OCONHC ₂ H ₅ OCOCH ₃ -C ₂ H, -CH ₂ CHCH ₂ - 8th OCOCH ₃ > CN

Table II (continued)

Y ₁

1 -H -H -H - H —CN —CN —N— C ₃ H ₇ 2 -CH ₃ -H -CH ₃ O —CN —CN -0- (CH ₂ J ₄ -O- 3 -OCH ₃ -OCH ₃ -OCH ₃ -OCH ₃ —CN —CN -0- (CH ₂ J ₄ -O- 4th -CH ₃ - H -CH ₃ - H - CN —CN . —N—
I. I.
CH ₃ 5 -CH ₃ .it -CH ₃ - H Carb
ethoxy Carb
ethoxy

—Η

TT

- Η

—Η

LT

TT

—CN —CN - (

—CN —CN - (

CH ₃

CH ₃

-NHCOCH ₃ -H

-NHQOCH ₃ —H —CN —CN -Q- (CH ₂ J ₄ -O-

B ei s 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- / 3-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 filtered off with suction and washed with benzene and im Vacuum drying cabinet dried at 50 °. The product is suspended in water and the suspension adjusted to pH 8 with sodium hydroxide solution; then the suspension is suctioned off and the residue with Water washed well. After drying, 215 parts (92%) of the product of the formula remain

H ₅ C, 0 *

".; _c ^ j _: ...; _{i {;} y _; - _; C ₂ H ₄ OC- (CH ₂ ) ₄ -COC ₂ H ₄ ; ; ;

CH

3.

150 parts of this product are in 190 parts by volume Dissolved dimethylformamide and added dropwise 109 parts by volume of phosphorus oxychloride to this solution at 15 to 20 ° C. with stirring, stirred at 95 ° for 1 hour and hot discharged with stirring onto 2500 parts of ice-water, where 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

C ₂ H ₅ H ₅ Q

NO ON

C ₂ H ₄ OC- (CH ₂ ) ₄ - COC ₂ H ₄

CH ₃

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 the bath of 95''C, cooled, the resulting orange precipitate sucked off and 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 "remains 31.4 parts (95.5%) of the color propanol 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

O — <f V-CH = C

C ₂ H ₄ OC- (CH ₂ ) ₄ - COC ₂ H ₄

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:

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

NC

C = CH

NC

C ₂ H ₄ OC COC ₂ H ₄

CH =

CN

COOC ₂ H ₅

was obtained as olive powder. It also dyes acetate and polyester materials in greenish yellow shades with excellent fast healing properties. Table III below includes a number of other valuable bis-styryl dyes obtained by esterifying 2 mol of the N- / f-oxyethylamines listed in column II with 1 mol of the dicarboxylic acid chlorides listed in column III, formylation according to Vi Ismeier and condensation the dialdehydes with 2 mol of a compound NC —CH ₂ —Y (where Y ₁ = Y ₂ ), analogous to the preparation instructions given in Example 6.

31 III 15 69 699 III 32 colour Tabel II Succinic acid dichloride greenish yellow N-ethyl-N - // - hydroxy-
ethyl aniline Terephthalic acid dichloride Y (Y ₁ = Y ₂ ) greenish yellow 1 N-butyl-N - ^ - hydroxy-
ethyl aniline Terephthalic acid dichloride - CN greenish yellow 2 N-ethyl-N - ^ - hydroxy-
ethyl-3-methyl-aniline Phthalic acid dichloride —CN greenish yellow 3 N-ethyl-N - ^ - hydroxy-
ethyl aniline Phthalic acid dichloride - CN greenish yellow 4th N-ethyl-N- / mydroxy-
ethyl aniline Oxalyl chloride - CN greenish yellow 5 N-ethyl-N - ^ - hydroxy-
ethyl-3-methylaniline Cyclohexane-1,2-dicarbon-
acid dichloride -COOC ₂ H ₅ greenish yellow 6th N-ethyl-N - ^ - hydroxy-
ethyl 3-methylaniline Maleic acid dichloride —CN greenish yellow 7th N-ethyl-N '/ i-hydroxy-
ethyl-3-methylaniline Isophthalic acid dichloride —CN greenish yellow 8th N-ethyl-N-zi-hydroxy-
ethyl-3-methylaniiine 1,2,5,6-tetrahydrophthalic acid
dichloride -CONH ₂ greenish yellow 9 N-ethyl-N - ^ - hydroxy-
ethyl-3-methylaniline Glutaric acid dichloride - CN greenish yellow 10 N-ethyl-B .- ^ - hydroxy-
ethyl-3-methylaniline Diglycolic acid dichloride - CN greenish yellow 11th N-methyl-N-ß-hydroxy-
ethyl 3-chloro-aniline Thiophene-2,5-dicarboxylic acid
dichloride -so ₂ - <3 ^> greenish yellow 12th N-ethyl-N-ß-hydroxy-
ethyl-3-methyl-aniline Thiophene ^ S-dicarboxylic acid
dichloride —CN greenish yellow 13th N-ethyl-N - ^ - hydroxy-
ethyl aniline Thiophene ^ S-dicarboxylic acid
dichloride —CN greenish yellow 14th N - ^ - cyanoethyl-N - ^ - hy-
hydroxyethyl aniline Thiophene-2,5-dicarboxylic acid
dichloride - CN greenish yellow 15th N-ethyl-N- / i-hydroxy-
ethyl-3-methyl-aniline Thiophene ^ S-dicarboxylic acid
dichloride - CN -.- ■ / '■;' ·. "j, '- *. greenish yellow 16 N-zZ-cyanoethyl-N - ^ - hy-
hydroxyethyl aniline Thiophene-2,5-dicarboxylic acid
dichloride —CN greenish yellow 17th N-ethyl-N-yz-hydroxy-
ethyl aniline Thiophene-2,5-dicarboxylic acid
dichloride - CN ■ ■■ ' greenish yellow 18th N-ethyl-N-zf-hydroxy-
ethyl aniline; ■■■ ". Thiophene-2,5-dicarboxylic acid
dichloride - CN '■■ "■' '·' ■" ■ ' greenish yellow 19th N-ethyl-N '/ i-hydroxy-
ethyl aniline Thiophene ^ S-dicarboxylic acid
■ ·; : dichloride -: -; ■; -COOC ₂ H ₅ greenish yellow 20th N-ethyl-N '/ Z-hydroxy-
ethyl aniline :,:;:, ■ _{; ::;} ..; ■ -, · Pyridine ^ .fi-dicarboxylic acid-
dichloride; =,; ι. _: , SO ₂ - ^ ~)> greenish yellow 21 N-ethyl-N '/ i-hydroxy- ,
ethyl aniline; - ..!;.) ■. ■ ' - ■ < ■ ■; '· ■■■■■■■ -CONH ₂ greenish yellow 22:, N-ethyl-N-7; -hydroxy-
iithyl-3-methyl-aniline : .--- ·, ΓΝ. ■ -, ί .-. ΊϊΊ ίίί "
..- ■, _.- · ■■. r -.Λ ί. "- ■ - · 23 ■ CN ■■ · ■ "· - ■■?; ° V ^J

COCI

Fortselziiim

III

Y (Y, = Y ₂ )

colour

24 N - ^ - cyanoethyl-N-p'-hy-
hydroxyethyl aniline O COCl - CN greenish yellow 5-nitro-isophthalic acid
dichloride 25th N-ethyl-N - ^ - hydroxy-
ethyl-3-methyl-aniline 5-nitro-isophthalic acid
dichloride —CN greenish yellow 26th N - ^ - cyanoethyl-N '/ i-hy-
hydroxyethyl aniline - CN greenish yellow Example 8 Example 9

One with that 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

NC

-2 ** 5

C = CH

C ₂ H ₄ OH

were in 20 parts by volume of benzene with stirring a solution of 1.1 parts by volume of succinic acid dichloride in 10 parts by volume of benzene and slowly added then heated to reflux with stirring for 1 hour and poured onto ice-water; it was extracted with chloroform, and the chloroform phase was with 10% sodium carbonate solution and then extracted with 2N hydrochloric acid, washed neutral with water, dried with sodium sulfate and evaporated. The remaining oil was dissolved in hot methanol / ethyl acetate. Crystallize after a while 3 parts of the dye that was already described in Example 1 Table ΙΪΙ as orange Product from.

In a 750 ml sulfonation flask 30 ml of phosgene are introduced 100 ml of dry chlorobenzene was added and at a temperature of -30 to -7O ⁰ C 1/10 mole of N- / i-hydroxyethyl-N- / 3-cyanoethyl-aniline in 50 ml of dry chlorobenzene were 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 in vacuo at 40 ° C. The product of the following formula is obtained

Analysis:

Calculated ...
found ....

NC

C ₂ H ₄ -CN

C ₂ H ₄ -OCOC ₂ H ₄

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 the dialdehyde is condensed with malodinitrile analogously to the procedure of Example 6, the dye of the following formula is obtained as an olive powder

C ₂ H ₄ CN

C = CH

■ NC

Example 10

To 100 parts of phosgene with saturated chlorobenzene 19 parts of N at 0 ⁰ C - ^ - Oxyathyl-N-ZJ-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. Keep stirring at this temperature for so long

C ₂ H ₄ -OCOC ₂ H ₄

Phosgene passed in until a clear solution has formed. Thereupon the excess phosgene with Blow out nitrogen and filter the hot solution. This solution becomes 19 parts of N - /? - Oxyethyl-N- / 3-cyanoethyl-aniline given and heated under reflux with stirring for 24 hours. Then the solvent is used completely removed in vacuo, added 10 ml of ethanol to the residue. After two or three Days, the backlog has for the most part become solid. After filtering off, the residue becomes

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

C ₂ H ₄ -CN NC-H ₄ C,

Analysis:

Calculated
found .

H ₄ L) C ~ OC ₂ H ₄

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 added at 15 to 20 ° C in a mixture of 9.2 parts by volume of dimethylformamide and 14.2 parts by volume of phosphorous oxychloride with stirring and then stirred for 6 hours at 60 ⁰ C, poured onto ice , Added chloroform and neutralized the mixture with sodium hydroxide solution. The chloroform phase is washed out with sodium chloride 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 the mixture is refluxed for 4 hours. The dye of the formula falls on cooling

NC

NC

C ₂ H ₄ CN

NCH ₄

C = CH

// V

// V

C ₂ H ₄ -OCOC ₂ H 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 slowly heated to 170 ° with stirring in an oil bath with 12.5 parts of diethyl carbonate and 0.2 parts of diethyl carbonate and 0.2 part of sodium, with ethanol being distilled off . After a while, the mixture is allowed to cool, the residue is taken up in benzene and extracted with water. The benzene phase is dried, the benzene is evaporated and the crude product is distilled. 18.2 parts of a pale yellow oil with a boiling point of 195 to 205 ^° C. at 0.02 Torr are obtained, which has the formula

C ₂ H 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 entered and at 15 to 2O ⁰ C with stirring in a Vilsmeier mixture of 18.6 parts by volume of dimethylformamide and 28.6 parts by volume of phosphorus oxychloride, then stirred for 5 hours at 60 °, on ice Discharged water, adjusted to pH 7 with sodium hydroxide solution, taken up in chloroform, washed the chloroform phase with sodium chloride solution, dried with sodium sulfate, concentrated. There remain 8 parts of the dialdehyde of the formula

/ V

CH ₁

C ₂ H ₅ H ₅

-N ■■ - ■ "■ O- N

\ "== ' ΊΙ ■■> .- ■' ■■■■■■ / ■ -

C ₂ H ₄ -OCOC ₂ H ₄

21 parts of the dialdehyde are dissolved in 300 parts by volume of methanol with 7 parts of malodinitrile and 0.5 parts of piperidine Heated under reflux for 4 hours, an orange crystalline precipitate soon forming. After cooling down at room temperature the product of the formula- ^ ■, ;;. · «;> -i ■; · ;; : 'ν

NC

NC

C = CH

H ₅ Q

CN

CH = C

CH,

CN

C ₂ H ₄ -OCOC ₂ H ₄

O
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 realness properties and good build-up ability.

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 in the bathroom heated to 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

C ₂ H ₅ H ₅ Q

O O N - ^^ S

C ₂ H ₄ -OC-NH-Jf X-NH-C-O-QH ₄

CH ₃

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

O QH ₅ H ₅ QO

ν λ ^ χ / \ j-χ y

C-f V-NO O N- <f V-C

H QH ₄ OCNH-Jj V-NHCOQH ₄ H

CH ₃

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

NC QH ₅ H ₅ Q CN

C = CH- <> -N O O N- <f> -CH = C

NC QH ₄ OCNH-J \ -NHC0QH ₄ 'CN

CH ₃

as an oil that 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.

B e i s ρ i e I 13

If you use 54 parts of N-ÄthyI-N - (/? - oxyäthyl) - 55 after cooling 46 parts of a crude product with

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. · -.;. ,,.

. C. Hj N Q H ₅ 10.6%; O NH (CI .U "-NH O
Il H ₅ C, "n . ( 10.5%. C- Il
-C- 0-C ₂ H ₄ ¹ 68.4. 8.8, H ₄ Analysis: '68.4. H 8.6. Calculated .. Il N found ... N

Formylicrl one 10.4 parts of this diurellian with a mixture of 18.6 parts 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

C ₂ H ₅ H ₅ C,

N O ON

C ₂ H ₄ OCN H (CH,) "N HCOC ₂ H ₄

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 ·> fancy brown-orange product of the formula

NC

NC

C = CH

C ₂ H ₅ H ₅ C _;

NO ON

\ Il Il /

C ₂ H ₄ OC NH (CH ₂ J 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 hamlets valuable bis-styryl dyes, which by condensation of 2 moles of those listed in column II N- / f-Oxyäthyl-amine with 1 mol of the in column III listed bis-isocyanates, formylation according to ViIs-

Meier and condensation of the dialdehydes with a 2 ·> 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. ,

Table IV II III V- NCO X colour N-ethyl-N - ^ - hydroxy-
ethyl-3-methyl-aniiine ToluyIcn-2,4-diisocyanate \ -NCO —CN yellowish
green I. N-ethyl-N-zMiydroxy-
ethyl-3-methyl-aniline Toluene-2,4-diisocyanate \ - NCO -COOC ₂ H ₅ yellowish
green 2 N-ethyl-N- / mydroxy-
ethyl aniline Hydroxane 1,6-diisocyanate > NCO —CN yellowish
green 3 N-methyl-N '/ Z-hydroxy-
ethyl aniline Hxane-1,6-diisocyanate —CN yellowish
green 4th N-methyl-N - // - hydroxy-
ethyl aniline Phenylene-1 ^ -diisocyanate —CN yellowish
green 5 N-methyl-N - / ^ · hydroxy-
ethyl aniline Phcny len-1,4-diisocyanate -COOC ₂ H ₅ yellowish
green 6th N-ethyl-N '/ i-hydroxy-
ethyl aniline Phenylcn-1 ^ -diisocyanate - CN yellowish
green 7th N- / i-hydroxyethyl
1,2,3,4-tetrahydroquinoline Phenyl-M-diisocyanal —CN yellowish
green 8th N-Ethyl-N-yZ-hydroxy-
ethyl aniline OCN - ^ "V-CH ₂ -C ^ -CN yellowish
green 9 N-ethyl-N - ^ - hydroxy-
ethyl-3-methyl-aniline OCN - {~ y-CH ₂ - <ζ - CN yellowish
green 10 N-ethyl-N-zf-hydroxy-
ethyl-3-methyl-aniline OCN- ^ y CU ₂ - {' COOC ₂ H ₅ yellowish
green 11th N-ethyl-N '/ i-hydiOxy-
ethyl 3-chloro-aniline OCN 4 \ CH ₂ 4. CN yellowish
green 12th 809 522 / Θ

41 42

Example 14

In 35.8 parts of N-ethyl-N-cy-oxyethyl-m-toluidine, methanol is distilled off. The residue with

the dissolved with heating 0.2 parts of sodium, then distilled under high vacuum. One receives the pro

41.4 parts of N-ethyl-N - ^ - carbomethoxyaniline added> product of the formula ^; ,
ben and slowly heated to 250 C while stirring,

CH ₅ H ₅ C

\ Il /

C ₂ H ₄ COC ₂ H ₄

as a colorless oil, bp _o , 185 to 195. This amine is formylated according to Vi 1 Meier 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
\ /
- N
\ H ₅ H; O C ₂ N - / ^
/ \ = ; ^ ch /
Q
\ Il
-c — o— _: H ₄ \ /
NC H ₄ - CN
/ \
C.
/ \
C ₂ \
CN

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

Claims (3)

by Claims: I. Water-insoluble styryl dyes of the formula NC R ₁ R ₂ C = CH-A ₁ -N — Rj —Z — R4 —N — A ₂ - Y ₁ ■■■ '"- ■■ CN where Ai and A _{2 are} unsubstituted or substituted by lower alkyl, lower alkoxy, halogen, phenoxy, thiophenoxyv trifluoromethyl, acetylamino or aminocarbonyl substituted p-phenylene groups, Ri and R _{2 are} hydrogen, alkyl with one to four carbon atoms, with halogen, hydroxy, methoxy as substituents , ethoxy, cyano, phenyl, Aceloxy, Cyanäthoxy, Cyanacetoxy, Benzuyloxy, ^Me: thylcarbamoyl, phenylcarbamoyl come into question, as well as /, - Carbo (methoxy, ethoxy or propoxy) ethyl (wherein the terminal alkyl group in / - / - position Can carry cyano or an amino group), (S- or; -Carbo- (methoxy- or ethoxy) -propyl, / i-acetyl- or Formyi) -aminoethyl, / i-acetoxyethyl, //, y-diacetoxypropyl, /; -Methanesulfonylethyl-, // - ethanesulfonylethyl, // - (p-chlorobenzenesulfonylethyl, / i-methylcarbamyloxyethyl, // - phenyl- ■ carbamyloxyethyl, ß- ( methoxy-, ethoxy- or -isopropyloxy-carbonyloxyethyl, y-acetamidyl, y-acetamidyl '- (p-Nitrophenoxy) -äthyl, // - (p-Hydroxyphenoxy) -äthy 1, / H / Z-AcetylathoxycarbonylJ -äthyl, / '- [/'"- {cyano, hydroxy, methoxy or acetoxy) ethoxycarbonyl] ethyl, // - carboxyethyl, v-aminopropyl, / i-diethylaminoethyl, rf-cyanoacetoxyethyl, benzoyloxyethyl and p-alkoxy - or phenoxybenzoyloxyethyl; or with Ai or A _{2 form} 2,2, ^ T-tetramethyl-l ^ S ^ -tetrahydroquinoline, 7-methyl-l, 2,3,4-tetrahydroquinoline or 1,2,3,4-tetrahydroquinoline; R ₃ and R _{4 are} alkylene groups with up to 4 carbon atoms, which can be substituted _by hydroxy, acetoxy or ethylcarbamyloxy, Z is - O— ^ -N- -. NH-. C ₁ -C ₃ alkyl
-NH-CH ₂ CH ₂ -NH- —Ν— I) 20th 30th i ") 40 4) R ₅ for branched or chain-like aliphatic zvyei.ivalent 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 mentioned in the description Hydrocarbon radicals with 7 to 15 carbon atoms, phenylene aromatic hydrocarbon radicals having 6 to 15 carbon atoms, and cyclohexylene; Z also the bivalent Remnants of the formulas;: ■■. ; '■; —C —O— 1 ti O —O — C— Il ο —O — c — o— ο - CO - NH - CO - NH - CO - CO - NH
—CO --- NH — CO— -CO-NH- ^ NH-CO
- CO — CO — NH or -X'-Z'-X'- -N-CH ₂ CH ₂ -N-CH ₃ CH ₃ S X means where X '= - O - or imino and Z' the acyl radical of an organic dicarbamic acid with 2 to 16 carbon atoms, an organic dicarbamic acid with up to 15 carbon atoms, a radical of the formula. - OCO- X '- R ₆ - X' - OCO- —Ο — CH ₂ CH ₂ —NH — CH ₂ CH ₂ —O— or the radical of the formula '—— O — R5 — ö—, wherein is where R _{6 is} an aliphatic or phenylene aromatic radical having 2 to 10 carbon atoms; or, when R ₃ and R ₊ ring through opening of oxirane _ ". see carboxylic acids with up to 3 carbon atoms or ethyl or phenylcarbamic acid are esterified N / A hydroxy, ethylene or propylene groups, an aliphatic or phenyl aromatic radical with up to 15 carbon atoms, which is optionally bonded on both sides via - O - and Y ₁ and Y _{2 are} cyano, Ci-C ^ -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 fibers containing ester groups, of polyacrylic fibers or for pigmenting high molecular weight organic material. ^; ' Älhylcarbamyloxy can be substituted, mean, Z is - O— —N— —S— -NH- C ₁ -C ₃ alkyl
-NH-CH ₂ CH ₂ -NH- —Ν—