DE1569674C - Styryl dyes - Google Patents

Description

The invention relates to dyes of the general formula I.

The dyes of the formula I can, for. B. by reacting aldehydes of formula II

; 0

15th

20th

CH ₇ ~ C

in the

X cyano, carbalkoxy with 1 to 2 carbon atoms in the alkoxy radical, Carbonamide, N-mono- or -dialkylcarbonamide with up to 4 carbon atoms, N-phenylcarbonamide, N-chloro-, N-methoxy- or N-methylphenylcarbonamide, N-dimethylsulfonamidophenyl or N-cyclohexylcarbonamide,

Y hydrogen, methyl, ethyl, methoxy or ethoxy,

Z hydrogen, chlorine, bromine, methyl, ethyl or trifluoromethyl,

R alkyl with 1 to 4 carbon atoms, / S-hydroxyethyl, ^ -Chloräthyl, ß-cyanoethyl, / 2-alkoxyethyl with a total of 3 to 6 carbon atoms, / 3-acetoxyethyl, benzyl, ß-phenylethyl or cyclohexyl and

R _{1 is} alkyl with 1 to 4 carbon atoms, cyclohexyl, benzyl, hydroxyalkyl with 2 carbon atoms or alkoxyalkyl with a total of 3 to 6 carbon atoms

means.

As a carbalkoxy and N-substituted carbonamide group for X are, for example, carbomethoxy, carboethoxy, N-methylcarbonamide, N-dimethylcarbonamide, N-butylcarbonamide, N-phenylcarbonamide, N- (p-methoxy-, p-chlorine-, m-chloro-, p-methyl) -phenylcarbonamide or N- (p-dimethylsulfonamido) phenylcarbonamide.

As substituents R are, for example, methyl, ethyl, propyl, iso-propyl, butyl, benzyl, /? - phenylethyl, cyclohexyl, / S-chloroethyl, / 3-cyanoethyl, /? - methoxyethyl, i / 3 _T butoxyethyl, / 3- Acetoxyethyl or / 3-Oxy ^ äthyl to be mentioned.

Examples of R ₁ that may be mentioned are methyl, ethyl, propyl, iso-propyl, n-, iso- or tert-butyl or cyclohexyl.

Technically particularly valuable dyes correspond of Formula V

55

60

in which Z is a hydrogen or chlorine atom or a methyl group, X is a cyano, carbomethoxy or carboethoxy group and R is an alkyl group with 1 to 4 carbon atoms, an / S-chlorine, / S-cyano, /? - methoxy or / J-acetoxyethyl group, a benzyl or / 3-phenylethyl group and R _{1 has} the meaning given.

OHC

with methylene compounds of the formula III

, CN

H ₇ C

be prepared, where X, Y, Z, R and R _{1 have} the meanings given.

Instead of the aldehydes of the formula II, the corresponding immonium salts of the formula can also be used IV

',O

CH ₂ CH ₂ C

use, in which R ₂ and R _{3 are} alkyl and R _{3 is} also a phenyl radical.
Aldehydes of the formula II are for example

p- (N-methyl-N- / 3-carbomethoxyethyl) -amino-

benzaldehyde,
p- (N-methyl-N - /? - carboHthoxyethyl) -amino-

benzaldehyde,
p- (N-ethyl-N- / S-carbomethoxyethyl) -amino-

benzaldehyde,
p- (N-Butyl-N - ^ - carbomethoxyethyl) -aminobenzaldehyde,

p- (N-cyanoethyl-N- / 3-carbomethoxyethyl) -. aminobenzaldehyde,
p- (N-iso-propyl-N- / S-carbobutoxyethyl) -amino-

benzaldehyde,
p- (N- / 9-chloroethyl-N-carboisobutoxyethyl) -

aminobenzaldehyde,
- p- (N-Ethyl-N - ^ - carbomethoxyethyl) -amino-

o-chlorobenzaldehyde,
p- (N-Butyl-N - /? - carboethoxyethyl) -aminoo-chlorobenzaldehyde,

p- (N-benzyl-N- / 3'-carboethoxyethyl) -amino- ; ·; '; .-, 3 ,, ;; o-chlprbenzaidehyd, -; !> ■ ·; ·; ■. ■; . * ·> ·.

p- (N - /? - Pheny]; äthyi; N- / 9-carbomethoxyethyl) -

amino-o-methylbenzaidehyd, p- (N-Butyl-N ^ -oätbbmethoxyäthyl) -amino-

o-methylbehzäldfeKyd ,; ^{; :} P- (N-methyl-N- / 9 carbornethoxyäthyl) amino

o-trifluoromethylbenzaldehyde, 4- (N-ethyl-N- _J 3-carbomethoxyethyl) -amino-

2-chloro-5-methoxybenzaldehyde, 4- (N-butyl-N- / 3-carboethoxyethyl) amino

2-methyl-5-ethoxybenzaldehyde, p- (N-methyl-N - /? - carbocyclohexyloxyethyl) -amino-o-chlorobenzaldehyde,

b / 4

p- (N - ^ - methoxyethyl-N-jS-carbomethoxyethyl) -

aminobenzaldehyde,
p- (N-butoxyethyl-N- | S-carbomethoxyethyl) -

aminobenzaldehyde,
p- (N-acetoxyethyl-N- / 3-carbomethoxyethyl) -

aminobenzaldehyde,
. p- (N- / J-hydroxyethyl-N - /? - carbobutoxyethyl) -

aminobenzaldehyde,
p- (N-methyl-N-ß-carbobenzyloxyethyl) -amino-

benzaldehyde or
p- (N-ethyl-N - /? - carbo- | jS-hydroxyethoxy] -

ethyl) aminobenzaldehyde.

Immonium salts of the formula IV are for example

p- (N-ethyl-N-jS-carbomethoxyethyl) -amino-

Ν ', Ν'-dimethylbenzaldimmonium chloride,
p- (N-Butyl-N - /? - carboethoxyethyl) -amino-

o-chloro-N ', N' -dimethylbenzaldimmonium-

chloride or
p- (N - /} - cyanoethyl-N-jS-carbomethoxyethyl) -

amino-o-methyl-N ^ N'-dimethylbenz-

aldimmonium chloride.

Compounds of formula IV are, for. B. after the Vilsmeyer reaction from the corresponding aniline derivatives and NiN-disubstituted amide chlorides accessible. On hydrolysis, one obtains from the compounds of formula IV the compounds of formula II.

As methylene compounds of the formula III are, for. B. malononitrile, methyl cyanoacetate, Ethyl cyanoacetate, cyanoacetamide, cyanoacet-N - methylamide, cyanoacetdimethylamide, cyanoacetanilide, Cyanacet-p-anisidid, Cyanaoet-p -chloranilid, Cyanacet-m-chloranih'd or Cyanacet-cyclohexylamid called.

A convenient procedure for preparing the compounds of formula I consists in the fact that compounds of the formula II in the presence or absence of solvents at temperatures from 20 to 150 ⁰ C, preferably 60 to 10Q ⁰ C, optionally with the addition of a condensing agent with compounds of formula III, implemented .;

Suitable solvents for the reaction are, for. B. Alcohols such as methanol, ethanol, butanol, glycol ether, such as glycol monomethyl ether, dioxane, tetrahydrofuran, benzene, chlorobenzene, toluene, dimethylformamide, Dimethyl sulfoxide, N-methylpyrrolidone or chloroform.

Suitable condensing agents to accelerate the reaction are, for example, piperidine, morpholine, Triethylamine, diethylamine, hexamethyleneimine, potassium hydroxide, sodium hydroxide, potassium alcoholate or sodium alcoholate.

■ The new dyes are suitable for dyeing and printing textile material made of polyesters, polyamides and especially cellulose and triacetate. The dyeings are distinguished by excellent lightfastness and very good fastness to washing and sublimation. The dyes are also excellent: for coloring, suitable at temperatures above ⁰ C 1OQ and let in blends of wool and polyester to wool undyed, i?. >;

On fiber materials made from cellulose triacetate, the new dyes in mixtures with "blue dyes of the anthraquinone series" produce green dyeings of "excellent lightfastness". l · ■ '' ■ '

The dyes also have good solubility in organic solvents and are suitable for Dyeing of paints, oils and synthetic fibers in bulk, as well as for dyeing polystyrene and polyethylene. The dyes are otherwise with fiber-forming polymers in organic solvents soluble and can be used in the usual way in spin dyeing processes.

Similar dyes which have an alkanoyloxy group in place of the carbalkoxy group are already known from the USA patents 2,583,551, 2,583,614 and 2,811,544. Compared to the known dyes, the new dyes have better drawability and better wet fastness properties on 27 ₂ acetate. In view of the structural similarity, this effect was unpredictable and surprising, especially because drawability and wet fastness are usually opposing properties, i.e. the better a dye is absorbed, the easier it is to remove it from the fiber, be it by washing or also Heat treatment (fastness to sublimation).

In the following examples, parts and percentages are based on weight ".

Example 1

117.5 parts of p- (N-ethyl-N- / 3-carbomethoxyethyl) aminobenzaldehyde and 36 parts of malononitrile are dissolved in 250 parts of methanol with the addition of 2 parts of piperidine heated to boiling under reflux for 1 hour. The crystallizes on cooling Styryl dye of the formula

H ₅ C ₂

H ₃ COC-CH ₂ -CH ₂

in yellow crystals. After recrystallization from methanol, the compound melts at 87 to OO ^.

The substance dyes polyester and polyamide fibers and triacetate silk in clear greenish yellow tones of very good light, wet and sublimation fastness properties.

100 parts of a fabric of Triacetatseide be heated in a dye bath containing 1.5 parts of said dye, 2 parts of the adduct of 47 mol of ethylene oxide with 1 mole of castor oil and 4000 parts of water, 45 minutes for 75 to 8O ⁰ C. A greenish yellow dyeing with very good light and wet fastness properties is obtained.

The aldehyde required for the synthesis of the dye is obtained in the following way: 140 parts of phosgene ^{are added at 0 to 5 ° C. to 95 parts of dimethylformamide in 500 parts of chloroform.} After stirring for 1 hour at room temperature, 207 parts of N - ethyl - N - β - barbomethoxyethylaniline are added; then the mixture is heated to 60 to 65 ° C. for 4 hours. The mixture is then poured onto 1000 parts of ice, made alkaline with 50% strength sodium hydroxide solution and extracted with chloroform. The chloroform layer is separated, dried and concentrated under reduced pressure. The distillation of the residue gives 160 parts (68% of theory) ρ - (N - ethyl - N - β - carbomethoxyethyl) - aminobenzaldehyde of boiling point 170 to 173 ° C / 0.1 Torr.

Example 2

32.6 parts of p- (N-iso-propyl-N - /? - carbobutoxyethyl) -o-chlorobenzaldehyde and 36 parts of malononitrile are refluxed for 2 hours in 200 parts of methanol. When cooling down the dye initially separates out as a viscous oil, which, however, crystallizes after a few hours. Man receives the styryl dye of the formula

(CH ₃ ) ₂ CH>

(H) H ₉ C ₄ O ₂ C-CH ₂ - CH /

N-

CH = C

, CN

-CN

Cl

in yellow crystals. The compound melts at 61 to 62 ° C.

The dye dyes polyester and polyamide fibers as well as triacetate silk in clear greenish yellow tones of very good light, wet and sublimation fastness properties.

100 parts of a polyester fiber material be of the sodium salt of a condensation product of / S-naphthalenesulfonic acid with formaldehyde, 1.5 parts of acetic acid and 3000 parts of water heated to 13O ⁰ C IV2 hours in a dye bath with 1.8 parts of said dye, 1.5 parts. A greenish yellow dyeing of very good fastness to light, washing and sublimation is obtained.

The aldehyde required to prepare the dye is prepared analogously to the Vilsmeyer reaction described in Example 1. It is obtained in 64% yield with the Kp. 200-205 ⁰ C / 0.05 Torr.

in yellow crystals. After recrystallization from methanol, the compound melts at 90 to 91 ° C. The substance dyes polyester and polyamide fibers and triacetate silk in clear greenish yellow shades of very good light, wet and sublimation fastness properties. 100 parts of a woven fabric of synthetic polyamide are heated for 1 hour at 90 ⁰ C in a dye bath consisting of 0.8 part of styryl, 2 parts of the sodium salt of Schwefelsäureesters of Ocenol and 4000 parts of water. A greenish yellow dyeing with very good wet fastness and sublimation fastness and good light fastness is obtained.

The representation of the preparation of the styryl dyes The aldehyde required is described in Example 1.

Example 4

132 parts of p- (N- £ -methoxyethyl-N- / 3-carbomethoxyethyl) aminobenzaldehyde and 60 parts of ethyl cyanoacetate are dissolved in 300 parts of dioxane with the addition of 2 parts of piperidine for 2 hours to 80 Heated to 85 ° C. After cooling, the styryl dye of the formula crystallizes

Example 3

CH ₂ H ₅ C ₂ -CN "■■■. ' / - "tr H ₃ CO ₂ -CH ₂ f .c-

CONH-

30th

117.5 parts of p- (N-ethyl-N- / 3-carbomethoxyethyl) aminobenzaldehyde and 95 parts of cyanoacet-p-anisidide are dissolved in 250 parts of methanol with the addition of 2 parts of piperidine heated to 60 to 65 ° C. for 1 hour. The styryl dye crystallizes on cooling formula

45 H3CO CH ₂ ~~ r CH ₂ \

NH ₃ CO ₂ C

CH ₂ '.

^L CH =

, CN

-CO ₂ C ₂ H ₅

35 in yellow crystals with a melting point of 100 to 101 ^° C.

The substance also dyes polyester and polyamide fibers as well as triacetate silk in greenish yellow tones very good wash, sublimation and light fastness properties.

The aldehyde required for the preparation of the styryl dye is as described in Example 1 Vilsmeyer reaction shown. It is obtained in 72% yield with a boiling point of 183 to 186 ° C / 0.02 torr.

Analogous to the working methods described, those listed in the following table can also be used Manufacture dyes that also produce greenish-yellow colorations: /

OCH,

No. X CN ·· ■ X -: ■■■ Z - ' CH ₃ ■ ■. ■■. ".> / ..:, :: ■; V- .. v. · ¹ '' ■ '. ^ ¹ ■; ■■. ■■. ■. 1 CN ■■ H '': ■ "■> '■■ H' : ch ₃ · -: '■■ ——> ^
• ■. ^J ■ ■■. ■: -. ■■ · ■■■■■ ■■: ■ .- · - ■■■■ - ■: ■■ CH ₃ : 2 CN : η ■ ;; · ^H? ; '-': CH ₃ ';:.:,.;,: ■,;. % C ₂ H ₅ ;;;. ■:;: ;;. 3 ■ ^cn:; - ■■■: ..- ■ -. ^: ■■ - H H ^CH 3:;:. nC ₄ H ₉ · ;; 4th . ■■■■■ CN: .-- ^, V '. .. '... _. H H C ₂ H ₅ . ,.,.; : 1-C ₄ H ₉ ■ / 5 cn '■' ^: "■ ·. ■ ·.; ■■■ ·. H H C ₂ H ₅ C ₂ H ₅ 6th H H '. 1-C ₄ H ₉

continuation

No. X CN Y ζ R. CH ₃ . CN H H 11-C ₄ H ₉ \ C ₂ H ₅ 8th cn; H H nC ₄ H ₉ UC ₄ H ₉ 9 CO ₂ C ₂ H ₅ H H HC ₄ H ₉ CH ₃ 10 CO ₂ C ₂ H ₅ H H CH ₃ CzH ₅ 11th CO ₂ C ₂ H ₅ H H CH ₃ HC ₄ H ₉ 12th CO ₂ C ₂ H ₅ ; H H CH ₃ 1-C ₄ H ₉ 13th CO ₂ C ₂ H ₅ ,: H H CH ₃ , C ₂ H ₅ 14th CO ₂ C ₂ H ₅ H H C ₂ H ₅ 1-C ₄ H ₉ 15th CO ₂ C ₂ H ₅ , H H C ₂ H ₅ CH ₃ 16 . CO ₂ CzH ₅ . H H WC ₄ K ₉ CzH ₅ 17th CO ₂ C ₂ H ₅ H H- HC ₄ H ₉ HC ₄ H ₉ 18th CN H H Ji-C ₄ H ₉ CH ₃ 19th CN. H H -CH ₂ ^ -CH ₂ CL nC ₄ H ₉ 20th CN H H -CH ₂ -CH ₂ -CE C ₂ H ₅ 21 CN. H H -CH ₂ -CH ₂ -CN C ₂ H ₅ 22nd CO ₂ C ₂ H ₅ ; H H -CH ₂ CH ₂ ^ ₃ -QCH CH ₃ 23 CO ₂ C ₂ H ₅ H H -CH ₂ -CH ₂ -Ci nC ₄ H ₉ 24 H H ~ - CH ₂ -CH ₂ Cl C ₂ H ₅ 25th CO2C2K5 H H -CH ₂ -CH ₂ -CN C ₂ H ₅ ' 26th CN H H -CH ₂ -CH ₂ -OCH ₃ CH ₃ Ή CN H Cl CH ₃ C ₂ H ₅ 2 & CN η ' Cl CH ₃ 11-C ₄ H ₉ 29 CN H Cl CH ₃ 1-C ₄ H ₉ 30th GN. . H. Cl CH ₃ C ₂ H ₅ 31 CN H Cl C ₂ H ₅ JC ₄ H ₉ 32 GN. H Cl C ₂ H ₅ .. · _{; ;} , .ν;,. CH ₃ 33 "CN:; ' .,; ',. H Cl nC ₄ H ₉ C ₂ H ₅ 34 "CN ■ ...; .. '' ⁱ '·' - ■:.;, H Cl Xi-C ₄ H ₉ nC ₄ H ₉ ■ 35 . CN H Cl UC ₄ H ₉ CH ₃ 36 CN H CH ₃ CH ₃ C ₂ H ₅ 37 cn,; ^: . H CH ₃ CH ₃ nC ₄ H ₉ 38 ' • CN -, ■ ;. : ... H CH ₃ CH ₃ iC ₄ H ₉ 39 , CN .., - '■ "- .: - H CH ₃ CH ₃ C ₂ H ₅ ,, 40 CN '"'"". ■ ■ H CH ₃ C ₂ H ₅ ■ i-C4H ₉ 41 '' "CN '. H CH ₃ ..; ■■: C ₂ H ₅ ; ..r-. . . , - '' y ^] - V-CH ₃ 42 . ·: CN λ; ϊ; : ν.φ. γ ΪΪ ■ - ■■: ■■ '' ■ H CH ₃ ■ .-'- 11-C ₄ H ₉ '■;-> - · - ■■■ C ₂ H ₅ 43 'cn : ■■><' ■ ' ^:: ■■ H CH ₃ ; ;.; ■■ ;; nC ₄ H ₉ : ■ _ ;; · ' - \ i ^ Ü._ :; '' - ⁿ "C4H ₉ 44. . -CO ₂ C ₂ H ₅ "^;.;-,:;. H CH ₃ 0.Vn-C ₄ H ₉ ■■■■ .. -, -: ■ - ■, ■ :.,; ■; -ίν; ί: CH ₃ 45 CO ₂ C ₂ H ₅ ;: " H Cl ί ' - .., CH ₃ - ■ - ■: - ^^ · ■■ ο -9 ² ^ ⁵¹ - 46. CO ₂ C ₂ H ₅ " H Cl ^ ₁ . CHU; - - ". ^ί ■ <l: -.- \ - r Ji-C ₄ H ₉ 47 ■ CQ ₂ C ₂ H _{51 f!} , ..., _. H Cl CH ₃ rr -. ^ ^C 4 ^H 9- ^: CO ₂ C ₂ H ₅ ; jxr: v:.: WV.r:., - / - ::. v / ■■. H Cl ^! ' ^ CH ₃ / -, -.-, -., Κ-, ι, ς ' J:;.> CzH ₅ · ■■ '49' "' '■:.' ■ H ■■■ ': ■ egg . • ■ _; - .. C ₂ H _5. ■: ... · ;::. '. ■? ^: -: χ ^ ώ, iC ₄ H ₉ ViOV Α ^ Γλ ^ 'Ϊ ^^' i - '^' ■ ^:: - ^: - ¹ ·· '- "'·"'■
Ι ^ ν ^. ^ Ν ^ τΓΙ «. ; t ■ _r . H he i C ₂ H ₅ ; .; ■ ;; ■■;.: - ^: CH ₃ ';, $'; '* "^ -> - Ii * - * IV ■ J. I Λ t ■ ΐ - * * t -
CO ₂ C ₂ H _{5 v} } i - ;: ·. · .. ·: -. ■. · Γ; ■ ■ - ■ Η- /. Cl ;; . UC ₄ H ₉ . , .-. ;; _: - C ₂ H ₅ '52 " - ν: Η · -. ^! ClV ^: UC ₄ H ₉ "- '

continuation

10

No. X CO ₂ C ₂ H ₅ Y Z R. nC ₄ H ₉ R, 53 CO ₂ C ₂ H ₅ H α CH ₃ nC ₄ H ₉ 54 CO ₂ C ₂ H ₅ H CH ₃ CH ₃ CH ₃ 55 CO ₂ QH ₅ H CH ₃ CH ₃ QH ₅ 56 CO ₂ C ₂ H ₅ H CH ₃ CH ₃ nC ₄ H ₉ 57 CO ₂ C ₂ H ₅ H CH ₃ QH ₅ 1-C ₄ H ₉ 58 ^; CO ₂ C ₂ H ₅ H CH ₃ QH ₅ C ₂ H ₅ 59! CO ₂ C ₂ H ₅ H CH ₃ HC ₄ H ₉ 1-C ₄ H ₉ 60 CO ₂ C ₂ H ₅ H CH ₃ nC ₄ H ₉ CH ₃ 61 CO ₂ C ₂ H ₅ H CH ₃ nC ₄ H ₉ QiHi 62 CN H CH ₃ CH ₃ HC) H ₉ 63 CN OCH ₃ H CH (CHa) ₂ CM ₃ 64 CONH-C ₆ H ₅ OCH ₃ Cl QH ₅ SQM ₅ 65 CONH '- \ / ^; - ^cl H H nC ₄ H ₉ QH ₅ 66 CONH - ^ ^ - OCH ₃ H Cl nC ₄ H ₉ HC ₄ H ₉ 67 CN H Cl CH ₂ 1 C ₆ H ₅ CH ₃ 68 CN H H ι_ιπ.2 ¹ ^ fI ₂ ^ gJrI ₅ CH ₃ 69 CO ₂ C ₂ H ₅ H Cl CH ₂ CH ₂ C ₆ H ₅ CH ₃ 70 CO-NH-CH ₃ H Cl CH ₃ QH ₅ 71 CONH - <^ hT)> H H QH ₅ CH ₃ 72 H H QH ₅

Claims (2)

Claims: 1. Styryl dyes of the general formula 40 45 OR ₁ 50 in the X Cyan, carbalkoxy with 1 to 2 carbon atoms in Alkoxy radical, carbonamide, N-mono- or -dialkylcarbonamide with up to 4 carbon atoms, N-phenylcarbonamide, N-chlorine, N-methoxy- or N-methylphenylcarbonamide, N-dimethylsulfonamidophenyl or N-cyclohexylcarbonamide, Y hydrogen, methyl, ethyl, methoxy or ethoxy, Z hydrogen, chlorine, bromine, methyl, ethyl or Trifluoromethyl, R alkyl with 1 to 4 carbon atoms, / 3-hydroxyethyl, / S-chloroethyl; ß-cyanoethyl, / S-alkoxyethyl with a total of 3 to 6 carbon atoms, / S-acetoxyethyl, Benzyl, / I-phenylethyl or cyclohexyl and Ri alkyl with 1 to 4 carbon atoms, cyclohexyl, Benzyl, hydroxyalkyl with 2 carbon atoms or alkoxyalkyl with a total of 3 to 6 carbon atoms means. 2. A process for the preparation of styryl dyes of the general formula according to claim 1, characterized in that there are compounds N λΟ ^ CH ₂ CH ₂ C OR ₁ with compounds of the general formula y CN H ₂ C X ' reacted, where X, Y, Z, R and R _{1 have} the meanings given for claim 1 · «. 3: The use of the dyes according to spoke 1 for dyeing or printing textile material made of polyesters, polyamides or cellulose £ -27z- or triacetate. J