DE1917456B - Naphthostyril dyes and their use for coloring textiles - Google Patents

Description

W-N-CO

in the presence of a condensing agent with a aromatic amine of the general formula

H ₇ N-

(HI)

converts, where W, Y, »and A are those given above Have meaning.

Examples of naphthostyrils of the general formula U are

HN- CO

HN-CO

The invention relates to new naphthostyril dyes of the general formula I.

45

W-N-C = N-A

(I)

in which W is a hydrogen atom, a low molecular weight alkyl radical, the / if-hydroxyethyl radical, a low molecular weight alkoxyalkyl radical, the / i-cyanoethyl, benzyl, cyclohexyl or phenyl radical, Y is a chlorine or bromine atom or a nitro, methyl or ethyl radical -, methoxy, methylmercapto or dimethylamino group and η is one of the numbers 0, 1 or 2, and the aromatic radical A is optionally substituted by 1 to 4 chlorine or bromine atoms or cyano, nitro, low molecular weight alkyl, trifluoromethyl, low molecular alkoxy, low molecular carbalkoxy, methylsulfonyl, phenyl, phenoxy, phenyl mercapto, anilino, benzthia optionally substituted by a mer

NO

SQM ₅

NO ₁

HN-CO

C ₂ H ₅ -N-CO

11-C ₃ H ₇ - Ν - CO

CNCH ₂ CH ₂ -N-CO

ιο

35

40

45

55

60

N-CO

OCH ₃
CH, - Ν — CO

CH ₁ OCH ₂ CH ₂ -N-CO

Cl
CH ₅ -N-CO

N (CH ₃ ) ₂

CH ₁ -N-Cu QH ''

HN-CO

SCH ₁

Examples of aromatic amines of formula III 15 are

NH ₅ -Z) -CN

NH, - / V- CN

CN

Cl Cl

NH ₂

CN

NH ₂ - \ / ~ ^CN

CN NH ₂ - / V-CN

Cl
Cl. Cl

NH,

Cl

CN
Cl

NH ₂ - /> -CN

CN NH ₂ - ^ ~ V ~ CN

CH ₃

NH ₂ Q NC

40

NH

NH

NH

NO ₂

NH, - / V-Cl

NO ₂

NH ₁ - /

CN NH ₂ - / ~~ V- CN

Br

Cl

Br

NH

NH

NH ₂ -

NH ₂

NH ₂

NH ₂ NH ₂

NH ₂ NH ₂ NH ₂

Cl

CH,

NO,

20th

_V ~~ V- COOCH ₃ - / ~~ S — COO-Bu

N-CH ₃

N-Bu

CO

- CH ₂ CH ₂

NH ₂

NH,

N ', ^s

N H

35

40

45

50

55

60

NH

-Of »

CO

NH

NH

V NH Λ NH 2 A. V I.
Br .τ

Br
Cl

Cl

NH, - / V NO ₂

NO ₂
NO ₂

Br

CN NO ₂ NO ₂ Cl NH ₂ - NO, I.
CN NH ₂ - <> NO ₂ p
CF ₃ NH ₂ - - / ~ V- NO ₂ Γ
CH ₃ NH ₂ - 3 ι
OCH ₃ OCH NH ₂ I.
OCH ₃

OC ₂ H ₅

NH ₂

55

60

CH ₃

NH ₂ - / "V-NO ₂ OCH ₃

NH,

NH ₁

NO,

SO ₂ CH ₃

NO,

COOCH ₃ CH ₃

/ V

NH ₂

NH,

H ₃ COOC OCH ₃

NO, COOC ₂ H ₅

NH,

NO,

35

40

45

5 ° NH,

Br

NH,

NO,

Br

OC ₂ H ₅

NH,

SO ₂ CH ₃

■ N = N-fV-NO ₂

CN

-N = N-

NO ₂

CH,

2,372

OCH

NH

CH,

NH

NH

OCH

NH, - <f V-N = N-

15th

Cl

OC ₂ H ₅ = N- > NO ₂ NH; OC ₂ H ₅ = N - CH
\ NO ₂ NH; CH O -0 2CH ₂ NH ₂ - OCH ₃
0-N = N 2CH ₂ OCH ₃ C. -N

25th

30th

35

40

The reaction of the aromatic amine (III) with the naphthostyril (II) can easily be carried out by stirring both reactants, preferably in an inert solvent in the presence of an acidic condensing agent, at an elevated temperature, preferably at 70 to 130 ^° C., for a few hours the used naphthostyril has disappeared.

As inert solvents in the condensation reaction, e.g. benzene, toluene, xylene, monochlorobenzene, Dichlorobenzene, nitrobenzene and carbon tetrachloride can be used.

As acidic condensing agents, for. B. phosphorus oxychloride, phosphorus tribromide. Phosphorus tri-chloride, Phosphorus pentachloride, aluminum chloride, thionyl chloride and sulfuryl chloride are used will.

After the reaction has ended, the product is obtained by cooling and then filtering the undiluted or obtained from the reaction mixture diluted with an alcohol. The product can also by neutralizing the acidic condensing agent and then removing the solvent can be obtained by steam distillation. If you have the product as a salt of an acid, e.g. B. as hydrochloride, obtained * so it is with a base, such as sodium hydroxide or an alkali metal carbonate, treated or dissolved in a base such as pyridine or triethylamine and then diluted with water, whereby the condensing agent can be easily removed.

A dye of the general formula I in which the Y substituents are halogen atoms is obtained by further treatment of the aforementioned condensation product, d. H. the one on Naphthostyril not halogen-substituted compound, with a halogenating agent by conventional methods. Further Naphthostyril compounds of the general formula I in which W is an alkyl or aralkyl radical are obtained by one of the following two processes: condensation reaction of an N-alkylated naphthostyril or N-alkylation of the naphthostyrile after the condensation reaction. Both methods provide the desired products.

The new dyes of the invention are used for dyeing and printing synthetic or semi-synthetic Textile goods, e.g. B. threads and fibers, or used for coloring plastics. she are particularly suitable for dyeing aromatic polyesters, polyamides, polyester ethers and polyurethanes and cellulose triacetate (acetyl cellulose). Especially textiles made from aromatic polyesters are made the dyes of the invention make it very light and sublimation-fast with high color yields and inexpensive Dyed levelness and high fiber affinity.

For dyeing, the dye of the invention is used together with a suitable dispersant, e.g. B. a condensation product of naphthalenesulfonic acid and formaldehyde, dispersed in water to produce a dyebath. In this dye bath z. Colored example textile material from an aromatic polyester after the high-temperature process at 120 to 130 ° C, after Trägerfärbeverfahren at 100 ° C or after thermosol at 180 to 210 "C, while Acetylcellulose- or Polyamidtextilgut is dyed at 85 to 100 ⁰ C. In the printing process, the textile material is printed with a printing paste containing the dispersed dye and then subjected to a heat treatment, which results in very lightfast and sublimation-resistant dyes.

By using an aromatic amine (Hl) with strongly electron-withdrawing groups as substituents X. such as a nitro group. you get Dyes, their practical use because of their high molar extinction coefficients and their great color fastness is associated with many advantages.

From the German Auslegeschrift 1 225 326 naphthostyril dyes are known, which are used for dyeing textiles from z. B. aromatic polyesters, synthetic polyamides, polyurethanes and cellulose triacetate are suitable. The dye prepared according to Example 1, first paragraph, was compared with the dye prepared according to Example 13 according to the invention with regard to its coloring properties! Textiles made of polyethylene glycol terephthalate compared. The brilliance of the coloring with the dye of the invention is much greater, the dye has a very attractive greenish yellow color while the dye of Example 1 is extremely dull because of its reddish yellow color

The examples illustrate the invention. Unless otherwise stated, parts are by weight. '' · '' ^:

2372

example 1

A mixture of 120 parts of monochlorobenzene, 20 parts of naphthostyril and 18 parts of p-nitroaniline is heated to 100.degree. To this mixture, 20 parts of phosphorus oxychloride are added dropwise over 30 minutes. The reaction mixture is heated to 100 ± 5 ° C. for 2 hours, then cooled to room temperature, and 30 parts of methanol are added dropwise. It is left to stand overnight, filtered and washed with methanol. Moist crystals are obtained. These are dispersed in 1,000 parts of water and the dispersion is made weakly alkaline with sodium hydroxide with thorough stirring.

It is then filtered, washed with water and dried. 29.4 parts of a yellow crystalline are obtained Compound with a melting point of 247 to 249 ° C, which probably has the following formula:

HN-C = N

NO,

The compound has a great affinity for polyester textiles and dyes them deep yellow, with the Color is very lightfast, sublimation fast and washfast.

Example 2

A mixture of 36 parts of monochlorobenzene, 6.0 parts Naphthostyril and 8.5 parts of 2-bromo-4-nitroaniline is heated to 100 ⁰ C. 6.1 parts of phosphorus oxychloride are added dropwise to the mixture over a period of 1 hour, and the mixture is _{heated to 100-110 ° C. for 3V for 2} hours. The reaction liquid is then allowed to cool. When the temperature has dropped to 60 ° C., it becomes 8 parts Methanol was added dropwise, and when 25 ° C. had been reached, the crystals were filtered off. They were washed with methanol and then with water. As soon as the washing liquid no longer had an acidic reaction, it was washed further with methanol and dried. 9.6 parts were obtained golden colored crystals with a melting point of 210 to 212 "C with the following structural formula

HN

NO ₂

Br

Found
calculated

C 55.1, H 2.78. N 10.8, Br 22.8; C 55.4, H 2.74, N 11.4, Br 21.7.

The dye dyes polyester textiles with a colourfast, yellow color.

Example 3

A mixture of 90 parts of monochlorobenzene, 15 parts Naphthostyril and 18.3 parts of 2-trifluoromethyl-4-nitroaniline is heated to 10O C ^1. In addition

To the mixture, 15 parts of phosphorus oxychloride are added dropwise over a period of 30 minutes. The reaction mixture is heated to 100 to 110 ° C. for 2 hours, then cooled to room temperature, and 30 parts of methanol are added dropwise. It is then filtered off and washed with methanol. Moist crystals are obtained which are dispersed in 1000 parts of water. The dispersion is made alkaline with sodium hydroxide with thorough stirring and then stirred ^{at 50 to 60 ° C. for a few hours.} As soon as no change in pH is found, the dispersion is filtered at an alkaline pH, washed with hot water and then dried. 23 parts of yellow crystals with a melting point of 239 to 241 ° C. and the following structural formula are obtained:

NO,

CF ₃

The dye stains
real, yellow color.

Polyester textile with color

Example 4

A mixture of 40 parts of monochlorobenzene, 5 parts of naphthostyril and 6 parts of 2-chloro-4-nitroaniline is heated to 90.degree. To the mixture, 5 parts of phosphorus oxychloride are added dropwise. The reaction mixture is heated for 2 hours at 90 to 100 ⁰ C, then cooled, diluted with 8 parts of methanol, filtered at 25 ° C and washed with methanol. The mixture is then washed thoroughly with a 1% aqueous sodium carbonate solution and then with water. After the dryer, a dye with a melting point of 20 (up to 208 ° C of the structural formula

HN-C =

Cl

The dye dyes polyester textiles with a real, yellow color.

Example 5

A mixture of 60 parts of monochlorobenzo, 10 parts of naphthostyril and 12.8 parts of 2,4,5-trichloroaniline is heated to 100.degree. The mixture is added dropwise with 10 parts of phosphorus oxychloride and heated to 100 ° C. for 2 hours. Once kei output Naphthostyril is no longer detectable, we cooled the mixture to 25 ⁰ C and treated with 40 parts methanol. It is then filtered, washed in methanol and the same alkali treatment as in Example 1 is carried out. You get a

2372

yellow dye from the melting point! 211 to 2I3 "C following structural formula:

Cl

HN-C = N ~ / ~ V-CI
Cl

IO

Example 6

A mixture of 100 parts of nitrobenzene, 5 parts of naphthostyril and 8 parts of an amine of the formula

NH,

CO '

N - CH ₂ CH ₂ CH ₂ CH ₃

20th

is heated to 100 ⁰ C, The mixture is treated dropwise with 5 parts of phosphorus oxychloride and heated for 1 hour at 90 to 100 ° C. After cooling, it is filtered, washed with water and then with methanol. The crystals obtained are dispersed in 300 parts of water, and the dispersion is brought by the addition of sodium hydroxide with thorough stirring at 5O ⁰ C to a pH value of eighth It is then washed, filtered and dried. 10 parts of a compound with a melting point of approximately 280 ^° C. are obtained with the following structural formula:

NCH ₂ CH ₂ CH ₂ CH ₃

HN-C = N

—P = M— P \ M =

N = N

The dye dyes polyester fabric with an orange color.

13 'j i s ρ i c I 8

a) A mixture of 100 parts of nitrobenzene and 10 parts of naphthostyril is heated to 50 "C, within 8.5 parts of bromine were added dropwise over a period of 30 minutes, followed by a temperature of 50 ° C. for 2 hours heated, then treated with 10 parts of p-nitroaniline and heated to 80 "C. The reaction mixture is added dropwise within 30 minutes with 10 parts Phosphorus oxychloride added. The mixture is heated to 80 to 85 "C for 3 hours. As soon as the reaction is completed, 20 parts of methanol are added dropwise. Then the reaction mixture filtered, washed and neutralized. A new dye with a melting point of 271 bis is obtained 273 ° C of the following structural formula:

HN-C =

NO,

This dye dyes polyester fabric in a yellow, lightfast color.

b) The above procedure is repeated, but instead of 8.5 parts of bromine there are 9.6 parts Sulfuryl chloride is used to obtain a similar dye with the following structural formula:

NO,

The dye dyes polyester fabric with light orange Color.

Example 7

A mixture of 30 parts of monochlorobenzene, 5.0 parts of naphthostyril and 6.4 parts of p-aminoazobenzene is heated to 100 ° C, within 30 minutes with 5.0 parts of phosphorus oxychloride dropwise added and then heated to 100 ± 5 ° C for 2 hours. Then it is cooled and dropwise mixed with 30 parts of methanol. The deposited crystals are filtered off and with Methanol washed. The moist filter material obtained is suspended in 200 parts of water, and the The suspension is made weakly alkaline by adding sodium hydroxide. It is stirred for a while the suspension is filtered and washed with water. After drying you get that Product in the form of orange crystals of the following structural formula:

Example 9

Example 8 is repeated, but N-methylnaphthostyiil is used instead of naphthostyril, whereby a dye of the following structural formula is obtained:

CH ₃ -N

NO,

60 This dye gives polyester textile a good reddish-tinged yellow.

Example 10

A mixture of 3.7 parts of 1,2-dihydro-2 - [(4'-nitro-2'-bromophenyl) imino] benz- [cd] indole. 4.7 parts of p-toluenesulfonic acid methyl ester, 11 parts of ethylene glycol monomethyl ether and 3.5 parts of potassium carbonate is gradually heated to 100 ⁰ C. The mixture is heated to 90 to KK) ¹¹ C for 1 hour and then cooled to 25 ° C. Then 10 parts of methanol are added dropwise. The deposited crystals

I 917456

are filtered off, with methanol and then with water washed and dried. A dye with a melting point of 186 to 188 "C is obtained Structural formula:

Br

IO

This dye dyes polyester textile a good reddish yellow.

Example 11

Example 10 is repeated, but instead of 4.7 parts of p-toluenesulfonic acid methyl ester 4.7 parts of benzyl bromide are used. A dye with the following structural formula is obtained:

<(~ \ -CH ₂ -UC = N- / "V-NO ₂

Br

zo

HN-C = N

NO ₂

CN

65

This dye dyes polyester textiles with a colorfast, brilliant yellow color.

10

Example 14

This dye turns plastics orange.

Example 12

A mixture of 5 parts of 6,8-dichloronaphthostyril, 3.8 parts of 2-cyano-4-nitroaniline and 40 parts of nitrobenzene is heated to 100 ° C, treated dropwise with 4 parts of phosphorus oxychloride and 3 hours heated to 100 to 115 ° C. Then the Mixture according to Example 1 worked up. Yellow crystals of a dye with a melting point are obtained approx. 270 ° C following structural formula:

A mixture uus 4 parts of the dye from Example 1.6 parts of sodium dinophthyl methane disulfonate and 20 parts of water is ground in a ball mill for 48 hours. The resulting colloidal Liquid is dried by spraying. Of the 10 parts of dye obtained, I part becomes in 1000 parts of water are dispersed, 25 parts of spun yarn made from a polyester are made for this fiirbath given, the bath is gradually heated. The dyeing process is carried out under pressure at 130 ° C within one hour. After dyeing, the yarn is washed with hot water, clarified and dried. A deep yellow colored product is obtained. This product is particularly light, sublimation and washable.

Example 15

From 4 parts of the compound of Example 8 a) is obtained by following the procedure of Example 14 10 parts of a dye. 1 part of it is used together with 4 parts of o-phenylphenol and 2 parts of acetic acid and 20 parts of a polyester spun yarn was added to 1000 parts of water. The dyeing process takes 90 minutes at 100 ° C. After dyeing, the yarn is washed with hot water, clarified and dried. A product with a deep reddish-tinged yellow color is obtained. It is particularly light, sublimation and washfast.

Example 16

CN

The dye dyes polyester textiles with a colorfast, brilliant yellow color.

Example 13

Example 10 is repeated, but instead of 5 parts of 6,8-dichloronaphthostyril, 3.8 parts of naphthostyril are used used. Yellow crystals of a dye of the following structural formula are obtained:

Following the procedure of Example 14, four parts of the above compound give 10 parts of one Dye.

A polyester fabric is made with a paste of 5 parts of this dye, 30 parts of water and 65 parts of a starch tragacanth thickener printed and then dried. Then the printed fabric heated to 200 ° C for 2 minutes, washed with water and clarified. A brilliant greenish yellow colored product is obtained Product that is particularly light sublimation and washfast.

Example 17

HN-C = N

NO ₂

Cl

To prepare a dyebath, 1 part of the above compound is dispersed in 1000 parts of water

20 parts of a cellulose triacetate fabric are placed in this dye bath and 1 hour at 100 ° ( colored. After dyeing, the fabric is washed in water, soaped, and again with water washed and dried. A colorfast, reddish-tinged yellow product is obtained.

19th

20th

Examples 18 to

clic the polyester textile used in Examples 14 to 16 tans well. The color oi lic are dyes, which are the following colored products in the right-hand column Irten compounds contain, used and given in the table below.

Structural formula of the connection

CF ₃

HN-C = N-

-NO,

HN-C = N

f / NO ₂ CH ₃ -N-

HN- C = N- <Y-NO ₂

CH

_ _N _C = N- / ~ \ -NQ:

Cl

hue

Reddish yellow

Reddish yellow

yellow

Light orange

Reddish yellow

Reddish yellow

Reddish gel

example

21

Continued (21

Structural formula of the connection

C ₂ H ₅ - -NC = N- ^ V- NO ₃

HN-C = N- <f S-NO

HN-C = N- / V-NO,

Cl

HN-C = N- <f V-NO ₂

■ A /%

i i

Br 22nd

Γ »rhi on

Reddish yellow

yellow

Brilliant green

Light yellow

Light yellow

Light orange

yellow

yellow

23

Continued 24

example

Structural formula of the compound hue

HN-C = N- <f VnO

SCH ₃

H ₅ C ₂

HN-C = N-fV-NO,

N (CH ₃ ),

OCH ₃ reddish yellow

yellow

Reddish yellow

orange

Reddish yellow

yellow

Reddish orange

Reddish yellow

25th

Continued 26

example

Structural formula of the compound hue

HN-C = N-Y ^ V-Cl

yellow

yellow

yellow

yellow

Brilliant yellow

Brilliant greenish yellow

yellow

yellow

• ■ 2372 V

27

Continued 28

example

Structural formula of the compound Color <

CH ₁ -NC = N SO ₂ CH ₃

orange

yellow

orange

yellow

HN-C = N

S V COOC ₂ H ₅

yellow

N-CH ₂ CH ₂ CH ₃

yellow

NCH ₂ CH ₂

Reddish

2372 V

29

Continued 30

Structural formula of the compound hue

HN-C = N-V ~ A-C ^

Cl

QH ₅ -N-C = N- / ~ V-CN

Ύ)

N (CH ₃ ),

CH ₁ -NC =

V-CH ₂ -N -C = N - <(V-CN

yellow

Reddish orange Reddish yellow Reddish yellow

yellow

orange

yellow

yellow

• 2372 V

Ιγ

I 917

Continued 32

example Structural formula of the connection

hue

H ₅ C ₂

HN-C = N

N = N

N (CH ₃ ) yellow

orange

orange

orange

Reddish orange

orange

orange

Reddish orange

example

33

continuation

34

Structural formula of the connection

HN-C = N

egg!.,

n = n / ~ Vn

OCH ₃ Cl

CH.,

CN

CH.-N-C =

yV

OCH ₃

NCCH ₂ CH ₂ -NC =

CH, -N-C = I

HN-C = N

Br hue

orange

Reddish yellow

Reddish orange

Reddish yellow

Reddish orange

orange

Claims (2)

Patent claims: I. Naphthostyril FurbslolTs the General formula W-N-C = N-A IO in which W is a hydrogen atom, a low molecular weight alkyl group, the // - hydroxyethyl group, a low molecular weight alkoxyalkyl group, the / i-cyanoethyl, benzyl, cyclohexyl or phenyl group, Y is a chlorine or bromine atom or a nitro, methyl or ethyl group -, methoxy, methylmercapto- or dimelhylamino group and η is one of the numbers 0, 1 or 2, and the aromatic radical A is optionally substituted by 1 to 4 chlorine or bromine atoms or cyano, nitro, low molecular weight alkyl, trifluoromethyl, low molecular weight alkoxy, low molecular weight carbalkoxy, methylsulfonyl, phenyl, phenoxy, phenylmercapto, anilino, benzthiazolyl, benzoxazolyl or benzimidazolyl group optionally substituted by a methyl group on the benzene nucleus, a phenyl or naphthyl radical optionally substituted by 1 to 4 chlorine atoms or cyano, nitro, low molecular weight alkyl, low molecular weight alkoxy, dimethylamino or morpholino groups, a further substituted radical of azobenzene or azonaphthalene ins, the remainder of a phenylenedicarboxylic acid-N-low molecular alkylimide or -N-phenylethylimide, the remainder of the acridone or the remainder of the anthraquinone. 2. Use of the dyestuffs according to Claim 1 for dyeing aromatic textiles Polyesters, polyurethanes, polyester ethers, synthetic polyamides or cellulose triacetate. zolyl, benzoxazolyl or benzimidazolyl group Phenyl or naphthyl radical, optionally with 1 to 4 chlorine atoms or cyano, Nitro, low molecular weight alkyl, low molecular weight alkoxy, dimethylamino or morpholino groups further substituted residue of azobenzene or azonaphthalene, the residue of a phenylenedicarboric acid c-N-low molecular weight alkylimide or -N-phenylethylimide, the remainder of the acridone or the remainder of the anhraquinone is. The naphthostyril dye is obtained in general Formula I, if you have a naphthostyril det general formula II