DE2637884A1 - ORGANIC COMPOUNDS - Google Patents

Description

SANDOZ-PATENT-GMBH
785O LBrrach

Organic compounds

The invention relates to new azo disperse dyes, their manufacture and use.

It has been found that the dyes of the formula I

D-N = N-K-N = [CHr — CR 6 i \ CHR) (D,

ORIGINAL INSPECTED 7Π9809/1176

- 2 - Case 150-3362 / A

where D is the remainder of a diazo component,

K is a 1,4-phenylene radical and the symbols R, independently of one another, denote hydrogen or C ₄ ~ alkyl.

The new disperse dyes naturally contain no substituents or atomic groups unsuitable for the person skilled in the art for disperse dyes, e.g. SuI-

Fonsäuregruppen or groups of the formula -0-C-O- or -O-C-N (.

Each substituent R, independently of the other substituents R, is preferably R ¹ , where R 'denotes hydrogen, methyl or ethyl, in particular hydrogen.

D is preferably referred to as D ', where D ^{1 is} phenyl bearing one, two or three substituents, including up to two each from the group consisting of chlorine, bromine, nitro and cyano and / or one each from the group C- - alkylsulfonyl , Aminosulfonyl, C '_ ₂ -alkylaminosulfonyl, di- (C, "~ alkyl) -aminosulfonyl, acetyl, trifluoromethyl and benzoylamino; 5-nitrothiazolyl-2; 4-methyl-5-nitrothiazolyl- 2} benzothiazolyl-2 or benzisothiazolyl-3, in which the benzene nucleus can carry one or two substituents, including up to two cyano or one chlorine, bromine, nitro, rhodane and methylsulfonyl; 1,2,4- or 1,3,4-thiadiazolyl-5 which is substituted by phenyl; 5-acetylthienyl-2; or S-methoxycarbonyl ^ -methyl-S-cyanthie-.nyl-2 means.

In particular, D has the meaning D ", which corresponds to the formula (II)

no na / 1 1 7 ß

- 3 - Case 150-3362 / A

wherein R is hydrogen, chlorine, bromine, cyano or nitro, preferably hydrogen, chlorine, cyano or Nitro,

R nitro, C "-alkylsulfonyl, aminosulfonyl, is 1— ^

C._ ₂ -alkylaminosulfonyl, di- (C .. "-alkyl) -aminosulfonyl, acetyl or benzoylamino, preferably nitro,
R ^ hydrogen, chlorine or bromine, preferably

Hydrogen,

R_ is hydrogen, chlorine, bromine, cyano or C ₁ _ -alkylsulfonyl, preferably hydrogen, chlorine, bromine, cyano or methylsulfonyl, but at least one of R 1 and R_ is hydrogen.

D /

K preferably has the meaning of K ¹ , which is unsubstituted 1,4-phenylene or 1,4-phenylene which is chlorine, bromine, methyl or a group of the formula -NHCOR ₈ in the 2-position and / or in the 5-position C _1-2 ^- AIkOXy carries.

R ₀ is hydrogen, C _1. , - alkyl, chloromethyl, bromomethyl, α- or ß-chloro or bromoethyl, ß-methoxyethyl, ethoxy- • methyl, C, ₂ ~ alkoxy, ß-chloroethoxy, ß-C, ^ Alkoxyethoxy, preferably R is hydrogen, C ₂ -alkyl or C, ₂ -alkoxy.

709809/1176

263788A

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D in formula (I) ^{is preferably D 1} , in particular D ″, K in formula (I) is preferably K ¹ and R is preferably R ¹ .

Particularly preferred compounds of the formula (I) correspond to the formula (Ia)

. ( Ζ " _ / f. / 0 - CHR ¹ \ y ₂ <α / CH ₂ - CR ^{1 X} CHR ·) ^(Ia) ' O ₀ N \ N = N - «( VR ¹ HC -O ^ Per- Γ
\ / ^R 9 ^R ll ^R 9 , Methyl, Acetylamino or wherein hydrogen

pionylamino, especially hydrogen or methyl,

R is hydrogen or C _1-3 -AlkOXy, in particular hydrogen,

R _{1 is} hydrogen, chlorine, bromine, cyano or methylsulfonyl, in particular hydrogen or chlorine,

R _{2 is} hydrogen, chlorine, cyano or nitro and R 'is hydrogen or C _n - alkyl, in particular

J. - ^ -

Mean hydrogen.

Particularly preferred compounds of the formula (I) are those of the formula (Ia) in which R ¹ , R _g and R _{1 are} hydrogen.

The new dyes of the formula (I) are prepared in a generally known manner, by diazotization of an amine of the formula D - NH »and coupling of the diazonium compound obtained with an amine of the formula (III)

709809/1 176

- 5 - Case 150-3362 / A

O - CHR

H-KrN (-CH ₂ - CR CHR

RHC - O

The compounds of the formula (III) are new and therefore also the subject of the present invention. Their production is characterized by the fact that one Compound of formula (IV)

HK- N (CH ₂ - CROH - CHR - 0 - CHR - CHRHaI) ₂ (IV),

where Hai is chlorine or bromine, at temperatures above 65 ° C in an aqueous or aqueous-alcoholic medium, in the presence of an acid-binding agent Means heated.

This reaction is preferably carried out in a methanol / water mixture at the boiling point. Suitable acid-binding agents are, for example, alkali metal hydroxides, especially potassium hydroxide. The compounds of the formula (IV) can be prepared by condensation of a primary amine of the formula HK-NH ₂ with the 2-chloro- or 2-bromoethylglycidyl ethers substituted according to the meaning of R, in the presence of a little water, at temperatures around 100.degree getting produced. The 2-chloro or 2-bromoethylglycidyl ethers substituted according to the meaning of R are known or can be prepared analogously to known methods.

The processing of the new compounds of the formula (I) into coloring preparations is carried out in a generally known manner, e.g. by grinding in the presence of dispersing and /

7,9809/1176

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or fillers. With the preparations, which may have been dried in a vacuum or by atomization, one can after adding more or less water, dye, pad or print in a so-called long or short liquor. The dyes pull out of aqueous suspension excellently on textile material made of fully synthetic or semi-synthetic, hydrophobic, high molecular weight organic substances. Particularly suitable they are used for dyeing or printing textile material made of linear, aromatic polyesters and cellulose-2 1/2 acetate, cellulose triacetate and synthetic polyamides.

It is colored or printed according to known methods, for example that in French patent specification No. 1.445.371 described procedure.

The dyeings obtained have very good all-round fastness properties; to be shown are the lightfastness, which Fastness to washing and dry cleaning.

It should also be noted that the new dyes have very good drawability and coloration with excellent sublimation fastness.

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

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B e i s ρ i e 1 1

173 parts of l-amino-2-chloro-4-nitrobenzene are dissolved in 250 Parts of concentrated hydrochloric acid and 350 parts of ice water and stirred at 0 ° to 5 ° with a solution of 69 Parts of sodium nitrite in 250 parts of water are diazotized. The diazonium salt solution thus obtained is with a Solution of 307 parts of N, N-di- (1,4-dioxany! Methyl) - -m-toluidine and 25 parts of urea combined in 350 parts of glacial acetic acid at 0 ° to 5 °. By adding sodium acetate until pH 4 is reached, the coupling is quickly brought to an end. The precipitated dye will filtered off, washed with water and dried. It dyes polyester fiber material in a brilliant, red shade with excellent fastness properties.

In the table below, further dyes of the formula (I) are indicated; they are denoted by the symbols K, D, R and its shade marked on polyester fiber material.

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Tabel

E.g.
No.

nuance

Cl

H ₃ CSO ₂ - (O

O ₀ N- (O) -

Cl

Cl 0,

O ₂ N- <O> -

H ₃ CC

Br

CN O,

H
H
H

HCOC ₂ H ₅

■ <ö> -

HCOCH ₂ Cl

OC ₂ H ₅

NHCOCH

[O) - ^J.
NHCOOCH ₃

3-CH.

orange do. do.

Red
brown purple

yellow
do. violet

navy blue do.

orange blue

709809/1

Case 150-3362 / A

E.g. No.

nuance

^C 6 ^H 5

N N

5 '^^ ^S

N-

Cl

, Cl

H ₅ C ₂ NHSO ₂ - (O) -

O ₀ N- (O) -

O.

H ₃ CSO ₂

HC-C-

CN

SO ₃ CH

NHCOCH.

do

do.

NHCOCH

^C 2 ^H 5

O)-

5,6-di-CH.

blue

Red

Scarlet fever

^C 2 ^H 5

O)-

Red

Red .

do.

purple

ruby

pink

blue

blue

do.

NHCOOCH ^ OCH-

709809/1176

Case 150-3362 / A

E.g

nuance

^C00CH

S "

NC

^ _n -N

NO,

NO,

do.

do.

blue

NHCOCK ₂ OC ₂ H

NHCOC ₂ H ₅

s?

CH ₃

O
Cl

NHCOCH

NHCHO

CH.,

orange

blue

6-C ₂ H ₅

violet

do.

blue

navy blue

do.

₂ CH ₂ CI

NHCOCH ₂ BzI
^OC 2 ^H 5

^lC 2 ^H S

do.

do.

do.

NHCOCHBrCH.

7 0 9 8 0 9/1

Case 150-3362 / A

Ex. No.

nuance

do.

CN Cl

Br

: n

Br

do.

do.

OCH,

κΟ

CH ₃

X) CH,

Φ "

* 3

3-CH.

ruby

do.

do.

Red

Brown

blue

do.

Red

709809/1

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Example of the manufacture of the clutch compo-

component of the formula N, N-di- (1,4-dioxanyl-

methyl) aniline ..

93 parts of aniline are mixed with 328 parts of 2,3-epoxypropyl-2'-chloroethyl ether and 5 "parts of water are stirred for 8 hours at 85 °. After cooling to 60 °, 500 parts of methanol are added added, the solution heated to boiling under reflux and over the course of 40 minutes with a solution of 224 parts of potassium hydroxide in 250 parts of water are added. After a further 40 minutes of refluxing, the Excess methanol is distilled off, 300 parts of water are added to the oily residue and the aqueous phase is separated off. The oily phase finally solidifies to form a crystal slurry which recrystallizes from benzene / cyclohexane will. The pure product melts between 111 and 113 °.

APPLICATION EXAMPLE

7 parts of the dye prepared according to Example 1 are mixed with 4 parts of dinaphthylmethanedisulfonic acid sodium, 4 parts of sodium cetyl sulfate and 5 parts of anhydrous sodium sulfate in a ball mill for 48 hours fine powder ground.

1 part of the dye preparation obtained in this way is made into a paste with a little water and the suspension obtained through a Sieve added to a dyebath containing 2 parts of sodium lauryl sulfate in 4000 parts of water. The liquor ratio is 1:40. 100 parts of cleaned polyester fabric are then added to the bath at 40-50 °, and 20 parts are added of a chlorinated benzene emulsified in water, heated

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the bath slowly to 100 ° and stains for 1-2 hours at 95-100 °. The red colored fabric is washed, soaped, washed and dried again. The level, strong coloring is excellent light, over-coloring -, - washing, water, sea water, sweat, sublimation, smoke gas, thermosetting, pleating and permanent press resistant.

709809/1176

Claims (16)

Claims I. The disperse dyes of the formula (I) D-N = N-K-N = r CHR> ^ V ^CHR J where D is the residue of a diazo component, K is a 1,4-phenylene radical and the symbols R, independently of one another, denote hydrogen or C 1 -alkyl. 2. The disperse dyes of the formula (I) according to claim (I), where D has the meaning of D ¹ and D ^{1 is} phenyl which bears one, two or three substituents, including up to two each from the group consisting of chlorine, bromine, nitro and cyano and / or one each from the group C 1-4 -alky ! sulfonyl, aminosulfonyl, C. -alkylaminosulfonyl, di- (C ₁ ~ -alkyl) -aminosulfonyl, acetyl, trifluoromethyl and benzoylamino; 5-nitrothiazolyl-2; 4-methy1-5-nitrothiazolyl-2; Benzothiazolyl-2 or benzisothiazolyl-3, in which the benzene nucleus can carry one or two substituents, including up to two cyano or one chlorine, bromine, nitro, rhodane and methylsulfonyl; 1,2,4- or 1,3,4-thiadiazolyl-5 which is substituted by phenyl; 5-acetyl-thienyl-2; or 3-methoxycarbonyl-4-methyl-5-cyanthienyl-2 is. 709809/1176 - 15 - Case 150-3362 / A 3. The disperse dyes of the formula (I) according to claim I, wherein D has the meaning of D "and D" has the Formula (II) corresponds wherein R. is hydrogen, chlorine, bromine, cyano or nitro, preferably hydrogen, chlorine, cyano or nitro,
R- nitro, C, "" alkylsulfonyl, aminosulfonyl, C ₁ "-alkylaminosulfonyl, di- (C ₁ " -alkyl) - JL- £ χ — ζ aminosulfonyl, acetyl or benzoylamino, preferably nitro / R ,. Hydrogen, chlorine or bromine, preferably ο Hydrogen, R is hydrogen, chlorine, bromine, cyano, or C, _ ₂ ~ alkylsulphonyl, preferably hydrogen, chlorine, bromine, cyano or methylsulfonyl, mean, but at least one of R and R_ is hydrogen. 4. The disperse dyes of the formula (I) according to claim I, in which K is the meaning of. K ¹ and K ^{1 have} unsubstituted 1,4-phenylene or 1,4-phenylene which is chlorine, bromine, methyl or a group of the formula -NHCOR ₀ in the 2-position and / or in the 5-position C _n -alkoxy ο X— / carries and R _g hydrogen, C, "-alkyl, chloromethyl, bromomethyl, α- or ß-chloro- or bromoethyl, ß-methoxy- 709809/1176 Case 150-3362 / A ethyl, ethoxymethyl, C _1-3 -AIkOXy, ß-chloroethoxy or ß-C, "alkoxy-ethoxy mean. 5. The disperse dyes of the formula (I) according to claim 1, wherein R has the meaning of R ¹ and R ^{1 is} hydrogen or C ₁ ″ -alkyl. 6. The disperse dyestuff according to claim 1, of the formula D ¹ -N = N- K ¹ -N [- 0 - CHR ¹ \ "CR ¹ CHR ¹ R ¹ HC-O / 2 wherein D ^{1 has} the meaning given in claim 2, K ^{1 has} the meaning given in claim 4 and R ^{1 have} the meaning given in claim 5. 7. The disperse dyestuff according to claim 1, wherein D ^{1 has} the meaning of D ", according to claim 3. 8. The disperse dyestuff according to claim 1, of the formula (Ia) R, N = N n [ch "- cr ¹ wherein R is hydrogen, methyl, acetylamino or propionylamino, especially hydrogen or methyl, 709809/1 176 26378Ö4 - 17 - Case 150-3362 / A R is hydrogen or C -alkoxy, in particular Hydrogen-,
R hydrogen, chlorine, bromine, cyano or methyl sulfonyl, especially hydrogen or Chlorine, R is hydrogen, chlorine, cyano or nitro and R ^{1 is} hydrogen or C "-alkyl, in particular Mean hydrogen. 9. The disperse dyes of the formula (Ia) according to claim 8, wherein each R ^{1 is} hydrogen, Rq is hydrogen or methyl,
R hydrogen and
R is hydrogen or chlorine. 10. The disperse dyestuff according to claim 8 or 9, wherein R and R are hydrogen. 11. A process for the preparation of the disperse dyes of the formula (I) according to claim 1, characterized in that an amine of the formula D - NH _{2 is} diazotized and the diazonium compound obtained with a compound of the formula (III) 0 - CHR HK-Nj -CH ₂ - CR CHR) (III) RHC - 0/2 clutch. 709809/1 178 Case 150-3362 / A 12. The compounds of the formula (III) according to claim 11. 13. Process for the preparation of compounds of the formula (III), according to claim 11, characterized in that a compound of the formula (IV) H-K-N (CH- CROH - CHR - 0 - CHR - CHRHaI) (IV), where Hai means chlorine or bromine, in an aqueous or aqueous-alcoholic medium, in the presence of an acid-binding agent at temperatures heated above 65 ° C. 14. Process for dyeing or printing fibers or Threads or materials made from them made of fully or semi-synthetic, hydrophobic, high molecular weight organic substances, characterized in that dyes of the formula (I) are used. 15. Use of the dyestuff according to claim 1 for dyeing or printing fibers or threads or made therefrom Materials made from fully or semi-synthetic, hydrophobic, high-molecular organic substances. 16. The materials dyed or printed with the dyestuffs according to claim 1 V ' 3700 / HW / HSc / MEW SANDOZ-PATENT-GMBH JULXL 709809 / 117g