CH594026A5 - Disperse dicyano styryl dyes - for (semi)synthetic matl esp arom polyester, cellulose acetates and polyamides (NL060476) - Google Patents

Abstract

Novel disperse dyes of formula (I) (where R1 is 2-8C alkylene or cycloalkylene; R2 is 1-10C alkyl (opt. substd. by alkoxy, alkylthio, alkylcarbonyloxy, or alkoxycarbonyl(oxy), cycloalkoxy, 3-10c alkenyl; R3 is H, halo, alkyl or alkoxy(carbonyl); R4 is halo, CN, CF3, cycloalkyl(thio), (cyclo)alkoxy,, (cyclo)alkylthio, phenyl(thio), phenoxy(alkyl), phenylthioalkyl, phenylalkyl, phenylazo, (cyclo)alkoxycarbonyl, phenylalkyltho, phenoxycarbonyl(oxy), benzoy(oxy) or phenylsulphonyloxy, or when R2 is alkyl, alkylthioalkyl or alkoxyalkyl with >6C, or alkenyl, then R4 may also be H; R3+R4 may complete a fused, 5 or 6 membered (un)satd. or aromatic, carbo- or hetero-cyclic ring; and R5 is H, Cl, Br, CH3 or CH3O; unless specified all alkyl and alkoxy have 1-4C and cycloalkyl have 5-8C; when R3 and R4 are alkyl or (cyclo)alkoxy they are opt. substd. by alkoxyncarbonyl) or phenyl; and when R4 is phenyl (-contg. gp.) this is opt substd. by is not >2 halo, CH, or alkoxy(carbonyl).) are used for dyeing, padding or printing (semi)synthetic, hydrophobic, high mol. wt. org. matls., esp. linear aromatic polyester, cellulose (2 1/2 or 3) acetate or synthetic polyamide. Dyeings have good general fastness, esp. towards sublimation and light; dyes are hydrolytically stable in the dye bath, have good resistance to redn. in presence of wool, and good reserve on wool and cotton.

Description

  

  
 



  It has been found that the styryl compounds of the formula I
EMI1.1
 where Rl is hydrogen, methyl or ethyl and R2 is a linear, branched or cyclic, optionally containing a C CC double bond and / or interrupted by an O- or -S-bridge, a linear, branched or cyclic aliphatic hydrocarbon radical containing 5 to 12 carbon atoms, excellent as disperse dyes , for dyeing or printing fibers or threads or materials made from them made from fully or semi-synthetic, hydrophobic, high-molecular organic substances.



  R2 preferably denotes a linear or branched Cs-e-alkyl radical whose chain is optionally interrupted by an oxygen or sulfur atom; in particular R2 is a linear or branched Cs-s-alkyl radical.



     Rl is preferably hydrogen.



   The process for the preparation of the new compounds of the formula list is characterized in that 1 mol of a compound of the formula II
EMI1.2
 where X is oxygen (preferably), or a radical of the formula = NR3, = [NsR3Riys or = (OR4) 2, R3 is hydrogen, Cl-alkyl or phenyl, R4 is Cl-alkyl and ye is an anion of an inorganic acid, with 1 mol Molononitrile condensed.



   The condensation (Knoevenagel reaction) is preferably carried out under weakly alkaline conditions, in the melt or in an inert, protic, preferably anhydrous solvent, e.g. B. methanol or ethanol. Alkalinity is achieved by adding a small amount of an organic base, e.g. Piperidine, pyrrolidine, triethylamine or triethanolamine. If a solvent is used, the condensation is generally allowed to proceed between 500 and 150 ° C., in particular at the boiling point of the solvent. The new compounds mostly precipitate during the course of the reaction or on cooling, otherwise they are obtained in a very pure state and in excellent yield by concentration, cooling and filtering off.



   The compounds of formula II are prepared by known methods, for. B. prepared from correspondingly R2 substituted 3- [N-p-hydroxyalkylamino] -l-methyl-benzene by reaction with phenyl isocyanate and introduction of the aldehyde group (Vilsmeyer reaction).



   The compounds of formula I are excellent disperse dyes. For use as such, they are usually processed into dye preparations in a known manner.



  This is done e.g. B. by grinding in the presence of dispersants and / or fillers. The preparations, optionally dried in vacuo or by atomization, can, after the addition of more or less water, be used for dyeing, padding or printing in what is known as a long or short liquor. The dyes are extremely well absorbed from aqueous suspension on textile material made of fully synthetic or semi-synthetic, hydrophobic, high molecular weight organic substances.



  They are particularly suitable for dyeing or printing textile material made from linear, aromatic polyesters and from cellulose 21/2 acetate, cellulose triacetate and synthetic polyamides. One dyes or prints according to known, z. B. the method described in French Patent No. 1,445,371.



   The dyeings obtained have good all-round fastness properties; The light fastness, the heat-setting, sublimation and pleating fastness are to be emphasized. They are good wet fast, e.g. B.



  water, sea water, washing and sweat-proof, solvent-proof, especially dry-cleaning-proof, lubricant, rubbing, dyeing, ozone, smoke gas and chlorine law; they are resistant to the effects of the various permanent pressing processes and the so-called soil release equipment.



  The resistance to reduction (when dyeing with wool) and the reserve of wool and cotton are good.



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



   example 1
12.0 parts of the aldehyde of the formula
EMI1.3
 obtained by reacting phenyl isocyanate with 3- (N-p-hydroxyethyl-N-n-octylamino) -1 -methylbenzene and subsequent aldehyde synthesis according to Vilsmeyer, are boiled with 2.2 parts of malonic acid dinitrile and 0.1 part of piperidine in 50 parts of ethyl alcohol for 5 hours under reflux cooling. After cooling in an ice bath and filtering, the crystalline dye of the formula is obtained
EMI1.4
  which is washed with a little ethanol and, processed into a dye preparation, dyes polyester fiber material in greenish-yellow shades with excellent fastness properties.



   The following table shows further dyes of the formula I according to the invention, which are prepared analogously to the procedure given in Example 1. All of these dyes dye synthetic fibers in greenish yellow tones.



   Table e.g. R1 R2 No.
EMI2.1


<tb>



   <SEP> 2 <SEP> -CR3 <SEP> nC7HIs
<tb> <SEP> 3 <SEP> - <SEP> C2Hs <SEP> n-C'His
<tb> <SEP> 4 <SEP> H <SEP> n-CsHt
<tb> <SEP> 5 <SEP> H <SEP> n-C9H19
<tb> <SEP> 6 <SEP> H <SEP> - <SEP> (CH2) 4CH (CH3) 2
<tb> <SEP> 7 <SEP> H <SEP> -CH2-O
<tb> <SEP> 8 <SEP> H <SEP> -CH (CH3tO-n-C4H9
<tb> <SEP> 9 <SEP> HIGH 3
<tb> 10 <SEP> H <SEP> -CHz-S-n-C4H9
<tb> 11 <SEP> H <SEP> - <SEP> C (CH3) <SEP> = <SEP> CH-C2H5
<tb> 12 <SEP> H <SEP> -CH = H)
<tb> 13 <SEP> H <SEP> -CR (CR) -n-CsRii
<tb> 14 <SEP> H <SEP> -CH2-O-CH (CH3) -C2H5
<tb> 15 <SEP> H <SEP> -CH2CH2
<tb> 16 <SEP> H <SEP> -CRCH (CH) -n-C4H9
<tb> 17 <SEP> H <SEP> - (CH2) 3-CH (CH3) 2
<tb> 18 <SEP> H <SEP> - (CH2) 5-O-C113
<tb> 19 <SEP> -CR3 <SEP> - <SEP> nCsHis
<tb> 20 <SEP> -CH3 <SEP> -CR (CRs) -n-C4H
<tb> 21 <SEP> H <SEP> - (CH2) 5-O-C2Hs
<tb> 22 <SEP> -CH3
<tb>
Table (continued) Example no.

  Rl R2 23 - C2Hs -CH (C2H5) -n-C4H9 24 -CR3 -CH2-O-CH2CH2CH (CH3) 2 25 -CR3-CR2-Sn-C4H9 26 -CR3 -CH = CH-CH2-S-C2H5 27 -C2H5 -CH (C2H5) 2 28 H -CH (n-C6H13) -O-C2H5 29 -C2H5
EMI2.2
 30 -C2H5 -CH2-O-C112-CH = CH-CH3 31 -C2H5 -CR (ClIs) -On-C4R9 32 -C2Hs -n-CsHti 33 -CH3 - (CH2) 5-O-C2H5 34 -C2H5 - (CR2) 5-O-CH3 35 H - (CH2) 3-CH = CH-CH3 36 H CH = CH-CH2-S-C4119
Application example
35 parts of the dye obtained in Example 1 are mixed with 30 parts

   sodium dinaphthylmethanedisulfonic acid, 35 parts of sodium lignosulfonic acid, 100 parts of water and 300 parts of silica-quartzite beads until the average diameter of the dye particles is less than 1. The dispersion is then filtered off from the siliquarzite beads, adjusted to pH 6.5 and spray-dried under mild conditions.



  1.0 part of the dye preparation obtained in this way is introduced into a dye bath which, adjusted to pH 5 with formic acid, is made up to 4000 parts with water. 100 parts of cleaned polyester fiber fabric are dyed at 130 for 1 hour in this liquor. After rinsing, soaping, rinsing and drying, a deep, level, brilliant greenish-yellow coloration is obtained, which has a very good level of general fastness.

 

Claims (1)

PATENT CLAIMS I. Process for the preparation of styryl compounds of the formula I. EMI2.3 wherein R1 is hydrogen, methyl or ethyl and R2 is a linear, branched or cyclic, optionally containing a C = C double bond and / or interrupted by a 0 - or - 5 - bridge aliphatic hydrocarbon radical containing 5 to 12 carbon atoms, characterized in that, that one mole of a compound of formula II EMI2.4 wherein X is oxygen or a radical of the formula = NR3, = [N3R3R4] ye or = (OR4) 2, R3 is hydrogen, Cl-6-alkyl or phenyl, R4 is Cl-6-alkyl and ye is an anion of an inorganic acid, with 1 mol of malononitrile condensed. II. The compounds of formula I, prepared by the process according to claim I. SUBCLAIMS 1. The method according to claim I, characterized in that a compound of formula II is used in which R2 is a linear or branched Cs-s-alkyl radical whose chain is interrupted by an oxygen or sulfur atom. 2. The method according to claim I or dependent claim 1, characterized in that compounds of the formula II are used in which Rl is hydrogen. 3. The method according to claim I, characterized in that a compound of the formula II is used in which R2 is a linear or branched Cs-s-alkyl radical. 4. The method according to dependent claim 3, characterized in that compounds of the formula II are used in which Rl is hydrogen.