KR800001532B1 - Process for preparing azo compounds - Google Patents

Abstract

Azo disperse dyes[(I; D = a diazo component for disperse dyes; K = 1,4-phenylene, 1,4-naphthylene; R1 = H, alkyl, Cl, Br, OH, phenyl; R2 = C1-4 alkylene, oxybis-C2-4 alkylene; X =-CH2-CR3 = CR3'-R4(R3, R3' = H, halogen; R4 = H, C1-4 alkyl) are prepd. by coupling diazonium deriv.(II) of amine with compd. III. Thus, 2-bromo-4, 6-dinitro aniline was added to conc. H2SO4 and 40% nitrosyl sulfuric acid was added this suspension. The mixt. was coupled in coupling agent which was composed of 5-acetyl-amino-2-epoxy-N-(3'chloropropen-2'-yloxy carbonyl-ethyl)-aniline dissolved in acetic anhydride to give disperse dyes IV.

Description

Manufacturing method of azo compound

The present invention relates to azo compounds, the synthesis of these compounds and the dispersion of dyes, and the present invention provides compounds of formula (I).

Wherein D is a group of diazo component of benzene, pyrazole, thiophene, thiazole, isothiazole, thiadiazole type, K is 1,4-phenylene or unsubstituted 1,4-naphthalene, K Is an unsubstituted 1,4-naphthylene, R ₁ is hydrogen or an alkyl group of (C ₁ -C ₄ ), and when K is 1,4-phenylene, R ₁ is hydrogen; Alkyl of (C ₁ -C ₄ ); Chlorine, bromine, vinylsulfonyl, hydroxy, cyano (C ₁ -C ₂ ) alkoxy, phenyl, acetylphenoxy, formyloxy, alkyl (C ₁ -C ₃ ) carbonyloxy, benzoyloxy, alkoxy (C _1- C ₂ ) carbonyl, alkoxy (C ₁ -C ₂ ) carbonyloxy, (C ₁ -C ₂ ) aminocarbonyl, di (C ₁ -C ₂ ) -alkylaminocarbonyl, or mono as -COOX Substituted (C ₁ -C ₄ ) alkyl; Substituted with another one by a hydroxy group is _{chlorine, (= (C 1 -C 4} )) alkoxy, hydroxy, phenoxy or substituted with any of the benzyloxycarbonyl (C ₁ -C ₄₎ alkyl; (C ₂ -C ₄ ) alkenyl; Or chloro- or bromo- (C ₃ -C ₄ ) alkel, R ₂ is straight or branched chain (C ₁ -C ₄ ) alkylene or

이며

And

인데, 상기에서 R₃와 R′₃중 하나가 수소이면 다른 하나는 할로겐이고 또 R₄는 수소 또는 (C₁-C₄) 알킬이며, T₁은 수소; (C₁-C₄) 알킬; 염소나 브롬으로 모노 치환된 (C₁-C₄)알킬이고; 페닐기; 염소, 브롬, 하이드록시, (C₁-C₂)알킬, (C₁-C₂)알콕시 또는 니트로에서 선택된 2개 까지의 치환제로 치환된 페닐이고 T₂는 수소; (C₁-C₄)알킬 또는 염소나 브롬, 또는 (C₁-C₄)알콕시기로 모노치환된 (C₁-C₄)알킬이며, U₁과 U₂는 각기 수소나 혹은 (C₁-C₄)알킬이며, U₃는 수소사

이며, 상기에서 U₁및 U₂가 함께 탄소원자와 결합하여 사이클로헥실환을 이루며, U₃는 수소, U₄는 수소, (C₁-C₄) 알킬 또는 알킬 (C₁-C₄)카보닐이다.or

Wherein one of R ₃ and R ′ ₃ is hydrogen, the other is halogen and R ₄ is hydrogen or (C ₁ -C ₄ ) alkyl, and T ₁ is hydrogen; (C ₁ -C ₄ ) alkyl; (C ₁ -C ₄ ) alkyl mono substituted with chlorine or bromine; Phenyl group; Phenyl substituted with up to two substituents selected from chlorine, bromine, hydroxy, (C ₁ -C ₂ ) alkyl, (C ₁ -C ₂ ) alkoxy or nitro and T ₂ is hydrogen; (C ₁ -C ₄₎ alkyl or chlorine or bromine, or (C ₁ -C ₄₎ alkoxy group and a mono-substituted (C ₁ -C ₄₎ alkyl, U ₁ and U ₂ are each hydrogen or or (C ₁ - C ₄ ) alkyl and U ₃ is hydrogen

In the above, U ₁ And U _{2 It} is combined with a carbon atom to form a cyclohexyl ring, U ₃ is hydrogen, U ₄ is hydrogen, (C ₁ -C ₄ ) alkyl or alkyl (C ₁ -C ₄ ) carbo Neal.

The compounds are not known to contain substituents or merged substituents on D or K (substituted 1,4-phenylene) and are known to cause steric or stability problems or adversely affect staining properties (eg, acetal groups).

It is preferred to contain unsubstituted alkyls such as R ₄ , T ₁ , T ₂ , U ₁ , U ₂ , and U ₄ , substituted alkyls such as T ₁ or T ₂ and one or two carbon atoms, in particular one carbon atom. Halogen means chlorine, bromine, fluorine or iodine, with chlorine and bromine being preferred.

The diazo component radical D is preferably D 'where D' is unsubstituted or chlorine, bromine, iodine (substituted up to 4 atoms each), nitro, cyano, methyl, trifluoromethyl, methoxy (C ₁ -C) ₂ ) alkylsulfonyl (substitutable up to 2 each), formyl, aminosulfonyl, alkyl (C ₁ -C ₂ ) carbonyl, alkoxy (C ₁ -C ₂ ) carbonyl, benzoyl, phenylalkyl (C _1- C ₂ ) carbonyl, phenoxycarbonyl, phenylsulfonyl, benzylsulfonyl, tolylsulfonyl, thiocano, (C ₁ -C ₂ ) alkyl- or di (C ₁ -C ₂ ) alkylaminosulfonyl, (C ₁ -C ₂ ) alkoxy (C ₂ -C ₄ ) alkylaminosulfonyl, (C ₁ -C ₂ ) alkoxy (C ₂ -C ₄ ) alkylaminocarbonyl-, phenylaminosulfonyl, N- (C _1- C ₂ ) alkyl-N-phenylaminosulfonyl, aminocarbonyl, (C ₁ -C ₂ ) alkyl- or di (C ₁ -C ₂ ) alkylaminocarbonyl, N- (C ₁ -C ₂ ) alkyl -N- phenyl-aminocarbonyl, phenylamino-carbonyl, phenyl, alkyl, - (C ₁ -C ₂₎ amino-carbonyl or phenyl-azo (values respectively to one Phenyl, phenyl-hexyl benzene azo group substituted at available) with a substituent selected from a 4 is unsubstituted or chlorine, bromine, (each be substituted up to 3), methyl, (C ₁ -C ₂₎ alkoxy cyano and nitro (each Unsubstituted or substituted with chlorine, bromine, nitro, cyano, methyl (up to two of each) phenyl, (C ₁ -C ₂ ) alkylcarbonyl, (C ₁ -C ₂ ) Thienyl substituted with alkoxycarbonyl (substitutable up to one each); Thiadiazolyl unsubstituted or substituted with phenyl, (C ₁ -C ₂ ) alkylthio or (C ₁ -C ₂ ) alkoxy; The following structural formula

Wherein d is hydrogen, (C ₁ -C ₂ ) alkyl, cyanoethyl, phenyl, chloro- or bromophenyl, or tolyl, and e is (C ₁ -C ₂ ) alkyl, (C ₁ -C ₂ ) Alkoxy, (C ₁ -C ₂ ) alkylthio, cyanomethyl, phenyl, alkoxy (C ₁ -C ₄ ) carbonyl, aminocarbonyl, (C ₁ -C ₂ ) alkylaminocarbonyl, di (C _1- C ₂ ) alkylamino carbonyl or N-alkyl (C ₁ -C ₂ ) -N-phenylaminocarbonyl and f is cyano or alkoxy (C ₁ -C ₂ ) carbonyl, unsubstituted or chlorine, bromine, nitro , Cyano (substituted up to 2 each), methyl, thiocyano, aminosulfonyl, (C ₁ -C ₂ ) alkylaminosulfonyl, di (C ₁ -C ₂ ) alkylaminosulfonyl, phenyl-aminosul Thiazolyl or isothiazolyl substituted with up to a total of 2 substituents selected from phonyl, N- (C ₁ -C ₂ ) alkyl-N-phenylaminosulfonyl, or alkylsulfonyl (substitutable up to 1 each).

More preferably when D is D ″, where D ″ is unsubstituted or chlorine, bromine, iodine, nitro, cyano, methyl, trofluoromethyl, methoxy (up to two of each can be substituted), (C ₁ -C ₂ ) alkylsulfonyl, tolylsulfonyl, aminosulfonyl, (C ₁ -C ₂ ) alkylaminosulfonyl, di (C ₁ -C ₂ ) alkylaminosulfonyl, phenylaminosulfonyl, N- (C _1- C ₂ ) alkyl-N-phenylaminosulfonyl, thiocyano or phenyl substituted with up to 3 substituents selected from phenylazo (one substituent each), benzenehex is unsubstituted or chlorine, bromine, Unsubstituted or substituted with up to three substituents selected from methyl, methoxy (up to two each), nitro or cyano (up to one each), unsubstituted or chlorine, bromine, nitro, cyano, methyl ( each be substituted up to 2)), phenyl, alkyl (C ₁ -C ₂₎ carbonyl, alkoxy (C ₁ -C ₂₎ or carbonyl (each 1 to one selected from the possible substitution) within Substituted with a substituent of up to 3-thienyl; Unsubstituted or substituted with up to 2 substituents selected from chlorine, bromine (substitutable up to 1 each), methyl, cyano, nitro or (C ₁ -C ₂ ) alkylsulfonyl (substituted up to 1 each) Diazolyl or isothiazolyl. Among D ″, unsubstituted or substituted phenyl is preferred. Most preferably when D is D ′ ″ where D ′ ″ is unsubstituted or in bromine, chlorine, iodine, nitro, cyano (up to 2 each), (C ₁ -C ₂ ) alkylsulfonyl Phenyl substituted with up to 3 substituents selected in total, with substituted phenyl groups being most preferred.

K is preferably K ', where K' is 1,4-napotylene or structural formula (IV).

R ₅ in formula (IV) is hydrogen, chlorine, bromine, (C ₁ -C ₂ ) alkyl, (C ₁ -C ₂ ) alkoxy, chlorine, bromine, hydroxyl, cyano, (C ₁ -C ₂ ) (C ₂ -C ₄ ) alkoxy or benzyloxy monosubstituted by alkoxy, (C ₁ -C ₂ ) alkoxy ethoxy or phenyl group and R ₆ is hydrogen, chlorine, bromine, cyano, (C ₁ -C ₂ ) Alkyl, (C ₁ -C ₂ ) alkoxy, formylamino, alkyl (C ₁ -C ₄ ) carbonylamino, chloro- or bromoalkyl (C ₁ -C ₄ ) carbonylamino, alkoxy (C ₁ -C ₂ ) -alkyl (C ₁ -C ₄ ) carbonylamino, alkoxy (C ₁ -C ₂ ) carbonylalkyl (C ₁ -C ₂ ) carbonylamino, alkoxy (C ₁ -C ₄ ) carbonylamino, phenoxy Cyalkyl (C ₁ -C ₂ ) carbonylamino, alkoxy (C ₁ -C ₂ ) alkoxy (C ₂ -C ₃ ) carbonylamino, alkoxy (C ₁ -C ₄ ) carbonylalkyl (C ₁ -C ₃ ) aminocarbonyl-amino, benzoylamino, phenyl-alkyl (C ₁ -C ₂₎ amino-carbonyl, phenoxy-carbonyl-amino, phenyl, alkoxy (C ₁ -C ₂₎ amino carbonyl, or (C ₁ -C ₂₎ Kilseol -5-phenyl ring is unsubstituted or both chlorine, bromine, iodine contained in the benzene nucleus, (C ₁ -C ₂₎ alkyl (each optionally substituted up to 2), (C ₁ -C ₂₎ alkoxy (only one of In this substitutable).

Wherein R ₅ is "together is preferably R ₅ where" R ₅ is hydrogen, (C ₁ -C ₂₎ alkyl or (C ₁ -C ₂₎ alkoxy.

More preferably R ₅ is R ₅ ″ wherein R ₅ ″ is hydrogen or (C ₁ -C ₂ ) alkoxy and most preferably (C ₁ -C ₂ ) alkoxy. R ₆ is R ₆ 'together are preferred where R _6' is hydrogen, chlorine, bromine, (C ₁ -C ₂₎ alkyl, (C ₁ -C ₂₎ alkoxy, formyl, amino, alkyl (C ₁ -C ₄ ) Carbonylamino, chloro- or bromoalkyl (C ₁ -C ₄ ) carbonylamino, alkoxy (C ₁ -C ₂ ) -alkyl (C ₁ -C ₄ ) carbonylamino, phenoxyalkyl (C _1- C ₄ ) carbonylamino, alkoxy (C ₁ -C ₄ ) carbonylamino, alkoxy (C ₁ -C ₂ ) alkoxy (C ₂ -C ₃ ) carbonyl amino, alkoxy (C ₁ -C ₄ ) carbonylalkyl (C ₁ -C ₃ ) aminocarbonylamino, benzoylamino, phenylalkyl (C ₁ -C ₂ ) carbonylamino, phenoxycarbonylamino, phenylalkoxy (C ₁ -C ₂ ) -carbonylamino, alkoxy ( C ₁ -C ₂ ) carbonylalkyl (C ₁ -C ₂ ) carbonylamino or (C ₁ -C ₂ ) alkylsulfonylamino.

More preferably when R ₆ is R ₆ ″ where R ₆ ″ is hydrogen, chlorine, bromine, (C ₁ -C ₂ ) alkyl, (C ₁ -C ₂ ) alkoxy or alkyl (C ₁ -C ₂₎ ) Carbonylamino group. Most preferably when R ₆ is R ″ ′ ₆ , where R ′ ″ ₆ is hydrogen, methyl or acetylamino.

K is preferably K ″ wherein K ″ is 1,4-naphthylene or a group of formula IV, wherein R ₅ in formula IV is R ′ ₅ and R ₆ is R ₆ ′. More preferred is the case where K is K ′ ″ where K ′ ″ is 1,4-naphthylene or a group of formula (IV) wherein R ₅ in formula (IV) is R ″ ₅ and R ₆ is R ₆ ″. Most preferably, where K is K ^IV , K ^IV is a group of formula IV wherein 1,4-naphthylene or R ₅ is (C ₁ -C ₂ ) alkoxy and R ₆ is R ₆ ′ ″.

R ₁ is preferably R ₁ ′ when K is 1,4-naphthylene, R ₁ is hydrogen or an ethyl group, and when K is 1,4-phenylene, R ₁ is hydrogen; Unsubstituted or hydroxy, cyano, (C ₁ -C ₂ ) alkoxy, formyloxy, alkyl (C ₁ -C ₃ ) carbonyloxy, benzoyloxy, alkoxy (C ₁ -C ₂ ) carbonyloxy or- (C ₁ -C ₄ ) alkyl mono-substituted by CO-OX; Hydroxy and chlorine, (C ₁ -C ₂ ) alkoxy, (C ₁ -C ₄ ) alkyl substituted with a second substituent selected from hydroxy, phenoxy and benzyloxy.

Most preferred R ₁ is the R ₁ ″ group, which is hydrogen or ethyl. R ₂ is' together are preferred where R _2, R ₂ is a linear (C ₂ -C _{4) alkylene, -CH (CH 3) -CH 2} -, -CH 2 -CH (CH 3) - or - CH ₂ CH ₂ -O-CH ₂ CH _2- .

Most preferably R ₂ is R ₂ ″ wherein R ₂ ″ is straight chain (C ₂ -C ₄ ) alkylene with 1,2-ethylene being particularly preferred. R ₃ and R ₃ 'is R ₃ a and R ₃ a' are preferred, and R ₃ a and R ₃ a 'is either chlorine or bromine and the other is hydrogen.

R ₄ is R ₄ 'together are preferred where R _4' is hydrogen or methyl.

T is T ₁ 'is preferable here T _1' is methyl, ethyl, chloro-or bromo-methyl, of the phenyl, or a chlorine, bromine, hydroxy, methyl, ethyl, methoxy, ethoxy or nitro to selected 2 Phenyl substituted by a substituent.

More preferably when T ₁ is T ₁ ″ where T ₁ ″ is hydrogen, methyl, chloromethyl or phenyl.

Most preferably when T ₁ is T ₁ ″ where T ₁ ″ ′ is hydrogen, methyl or phenyl.

T ₂ is T ₂ 'are preferred, and where T _2' is hydrogen, methyl, ethyl, chloro-or bromo-methyl or (C ₁ -C ₄₎ alkoxymethyl. More preferably T ₂ is T ₂ ″ wherein T ₂ ″ is hydrogen, methyl or chloromethyl and especially hydrogen is preferred. U ₁ and U ₂ is a preferably U ₁ 'and U _2', and where U ₁ 'and U _2' are each hydrogen or methyl, particularly preferably a hydrogen.

U ₃ is U ₃ 'are preferred, and where U _3' is hydrogen, (C ₁ -C ₂₎ alkoxymethyl, (C ₁ -C ₂₎ alkoxy -CH (CH ₃₎ -, acetoxymethyl or acetoxy - CH (CH ₃ )-.

X is preferably X ', where X' is a group of the formulas (a), (b) or (c), where R ₃ and R ' ₃ are R ₃ a and R' ₃ and R ₄ is R ' ₄ And T ₁ and T ₂ are T ′ ₁ and T ′ ₂ , but more preferably T ″ ₁ and T ″ ₂ and most preferably T ″ ′ ₁ , U ₁ and U ₂ are U ′ ₁ and U ′ _{2 is} preferably hydrogen and U ₃ is U ′ ₃ . More preferably X is X ″ where X ″ is a group of structural formulas (a) or (c). Most preferably X is X ″ ′ where X ″ ′ is the structural formula (a) or (c) in which R ₃ and R ′ ₃ are R ₃ a and R ′ ₃ a, R ₄ is R ′ ₄ , U ₁ and U ₂ are U ′ ₁ and U ′ ₂ are and preferably hydrogen and U ₃ is U ′ ₃ .

Preferred compounds of formula (I) are those wherein D 'is preferably D', more preferably D ″, K is K'1, preferably K ″ and more preferably K ″ ', most preferably K ^IV and R ₁ is R ′ ₁ , preferably hydrogen or ethyl and R ₂ is R ′ ₂ , preferably straight chain (C ₁ -C ₄ ) alkylene, more preferably 1,2-ethylene and X Is X ′ or X ″, preferably X ″ ′.

The present invention provides a method for preparing the compound of formula (I), characterized by coupling a diazonium derivative of the amine of formula (II) with a compound of formula (III).

R ₁ , R ₂ and X in the above structural formula are as defined above.

Coupling and diazotization reactions can be carried out according to conventional methods.

Coupling components wherein X is a group of formula (a) or (b) may comprise: a) condensation of an ester of formula (V) or (VI), (XI) or (XII) with an amine of formula (VI); Preference is given to condensation of the compounds of formula (VIII) or functional derivatives thereof, preferably acid chlorides with alcohols of formula (IX) or (XIII).

Here “hal” is chlorine or bromine.

The coupling component in which X is formula (a) or (b) is a one-step process, i.e., the addition of the amine of formula (VIII) in the presence of an excess of alcohol of the formula (IX) or (XII) Or the compound of formula (V) is condensed in anhydrous medium in the presence of a compound of formula (X) or (XIV), preferably in the presence of an acid acceptor (e.g. an aliphatic or heterocyclamine) or the amine of structure Or by addition reaction with crotonic acid, optionally in the presence of a catalyst such as Lewis acid or glacial acetic acid, and optionally diluting the reaction product with an organic solvent and adding a compound of formula (X) or (XIV) and an acid binder.

“Hal” in the above is chlorine or bromine.

All of these reactions can be carried out similarly to known methods. Alcohols of formula (IX) can be prepared by known methods, ie, analogous methods of hydrolysis of compounds of formula (X). The compounds of the formulas (V), (VI), (VII), (X), (X), (XI), (XII), (XIII) and (XIV) are known or readily available starting materials. It can be prepared similarly to the known method.

The coupling component of formula (III), wherein X is a group of formula (c), can be prepared according to a known method, i.e., a method in which an ester of formula (XV) is reacted with a compound of formula (III) in the presence of an acid binder.

Here “hal” is chlorine or bromine.

Esters of formula (XV) can be conveniently prepared by condensing a compound of formula (XVI), preferably an acid chloride or bromide thereof, with an alcohol of formula (XVIII).

Here “hal” is chlorine or bromine.

Structural formulas (XVI) and (XVII) compounds are known or can be prepared according to known methods.

Compounds of formula (I) are effective for the dyeing or printing of textile substrates containing synthetic, semisynthetic, high molecular weight, hydrophobic organic materials from aqueous suspensions. Preferred substrates are linear, aromatic polyester, cellulose 21/2 acerate, cellulose triacetate or synthetic polyamides.

The compound is made into a dye by grinding or spray drying in a vacuum or non-vacuum, for example in the presence of a dispersant and / or filler in accordance with conventional methods.

Dyeing can be carried out according to known methods.

[Reference. French Patent No. 1,445,371]

The dyes obtained have excellent remarkable fastnesses, in particular fastness to light, passion ignition, sublimation, compression and moisture.

In some cases, dyes of thermally unstable form may be converted into dyes of thermally stable form by known methods. Thermally stable forms have improved dyeing properties.

The following examples illustrate the invention.

Where parts are parts by weight and temperatures are in degrees Celsius.

Example 1

The manufacturing method of the dye of the said structural formula is as follows. 52.4 parts of 2-bromo-4,6-dinitroaniline are added to 220 parts of concentrated sulfuric acid with stirring, followed by cooling to 10 ° C. and 18.8 parts of 40% nitrosilsulfate over 35 minutes to the suspension. After stirring for 2 hours, the mixture was cooled with ice for 30 minutes, and then 5-acetyl-amino-2-epoxy-N- [3'-chloropropene- (2 ')-yloxycarbonyl-ethyl] was added to 180 parts of glacial acetic acid. Add diazonium salt to the coupling solution of 68.1 parts of aniline. After complete coupling, the reaction mixture is diluted with 1000 parts of ice-water and stirred for one hour, and the residue is filtered and washed with acid. The dye is then added to 5000 parts of water, stirred at 90 ° C. for 3-4 hours, washed with water and dried. The resulting product dyes the polyester fibers in pure dark blue.

Said coupling component can be manufactured as follows. 4 parts of 4-methoxyphenol, 144 parts of acrylic acid and 200 parts of acetone are added to the reaction vessel, followed by adding 240 parts of triethylamine. The mixture is stirred well while cooling so that the temperature does not exceed 50 ° C. After addition of cis and trans-1,3-dichloropropene-1225 parts, the reaction mixture was stirred at 50 ° C. for 6 hours, the resulting triethylamino-hydrochloride was filtered off and the filtered solution was 73 ° to 75 °. Vacuum distillation at 18-19 toro at < RTI ID = 0.0 > 35.6 parts of the obtained acrylic acid ester are mixed with 39.8 parts of 5-acetylamino-2-ethoxyaniline, 10 parts of glacial acetic acid, 0.4 part of zinc chloride and 0.2 part of 4-methoxyphenol and stirred at 110 to 115 ° C. for 5 to 6 hours. 5-acetylamino-2-ethoxy-N- [3'-chloropropene- (2 ')-yloxycarbonyl-ethyl] -aniline obtained after cooling can be dissolved in 100 parts of glacial acetic acid and used directly for dye production. have.

Example 2-7

Coupled below with the method described in Example 1, instead of 5-acetylamino-2-ethoxy-N- [3'-chloropropene- (2 ')-yloxycarbonylethyl] -aniline Ring component equivalents are used to obtain dyes with staining and color similar to those of Example 1.

EXAMPLE

2. 5-acetylamino-2-methoxy-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

3. 5-propionylamino-2-ethoxy-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

4. 5-propionylamino-2-methoxy-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

5. 5-acetylamino-2-ethoxy-N-ethyl-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

6. 5-acetylamino-2-methoxy-N-ethyl- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

7. 5-acetylamino-2-methoxy-N-propyl-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

8. 5-acetylamino-2-methoxy-N-butyl-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

9. 5-acetylamino-2-ethoxy-N- (prop-2′-yloxycarbonylethyl) -aniline.

10. 5-Acetylamino-2-ethoxy-N- (4′-methoxybut, -2′-ynyloxycarbonylethyl) -aniline.

11. 5-Acetylamino-2-methoxy-N- (4′-ethoxybut-2′-ynyloxycarbonylethyl) -aniline.

12. 5-acetylamino-2-ethoxy-N- (2′-chloropropene-2′-yloxycarbonylethyl) -aniline.

13. 5-acetylamino-2-methoxy-N- (2'-bromopropene-2'-yloxycarbonylethyl) -aniline.

14. 5-acetylamino-2-ethoxy-N- (3'-chloropropene-2'-yloxycarbonylethoxyethyl) -aniline.

15. 5-Acetylamino-2-methoxy-N- [β- (3′-chloropropene-2′-yloxycarbonyl) -β-methylethyl] -aniline.

16. 5-Acetylamino-2-methoxy-N- [W- (3′-chloropropene-2′-yloxycarbonyl) -butyl] -aniline.

17. 5-Acetylamino-2-ethoxy-N- [W- (3′-chloropropene-2′-yloxycarbonyl) -brofil] -aniline.

Example 18-51

2-chloro-4,6-dinitroaniline or 2-iodine-4,6-dinitroarline instead of 2-bromo-4,6-dinitroaniline used in Example 1-17 Dye is obtained by the method of 1. The dyes obtained also dye polyester fibers dark blue.

Example 52

17.2 parts of 2-chloro-4-nitroaniline are stirred with a mixed solution of 60 parts of water and 40 parts of concentrated hydrochloric acid at room temperature for 3 hours. The suspension is cooled by adding 100 parts of ice and diazotized with 7 parts of NaNO ₂ and 100 parts of water for 2 hours at 0-5 ° C. After reacting for another 30 minutes, excess sodium nitrite is removed by adding aminosulfonic acid. The resulting diazonium salt solution was filtered to give 100% of 40% glacial acetic acid in 3-acetylamino-N- (2'-cyanoethyl) -N- (3'-chloropropene-2'-yloxycarbonylethyl). -35 parts of aniline solution is added dropwise for about 30 minutes. After completion of the coupling reaction, the mixed solution is neutralized with sodium hydroxide and heated at 90-95 ° C. for 2-3 hours. The solution is filtered, the salt is washed and dried. The dye obtained has the following structural formula and dyes the polyester fibers in red.

Example 53-71

Similar to the method of Example 52, diazotized 2-chloro-4-nitroaniline is coupled with the coupling components listed below. The dye obtained dyes the polyester fibers in a similar phase as in the dye of Example 52.

53. 3-acetylamino-N-β-cyanoethyl-N- (prop-2'-ynyloxycarbonylethyl) -aniline.

54. 3-acetylamino-N-ethyl-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

55. 3-acetylamino-N-ethyl-N- (2'-brofen-2'-yloxycarbonylethyl) -aniline.

56. 3-Acetylamino-N-β-hydroxyethyl-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

57. 3-acetylamino-N, N-di- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

58. 3-acetylamino-N, N-di- (2'-chloropropene-2'-yloxycarbonylethyl) -aniline.

59. 3-acetylamino-N, N-di- (prop-2′-ynyloxycarbonylethyl) -aniline.

60. 3-acetylamino-N, N-di- (4'-methoxybut-2'-ynyloxycarbonylethyl) -aniline.

61. N-β-cyanoethyl-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

62. N-ethyl-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

63. N-β-hydroxyethyl-N- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

64. N, N-di- (3'-chloropropene-2'-yloxycarbonylethyl) -aniline.

65. N, N-di-prop-2'-ynyloxycarbonylethyl) -aniline.

66. N, N-di- (ynyloxycarbonylethyl) -aniline.

67. N-β-cyanoethyl-N- (prop-2'-ynyloxycarbonylethyl) -aniline.

68. N-β-hydroxyethyl-N- (prop-2′-ynyloxycarbonylethyl) -aniline.

69. N-ethyl-N- (prop-2′-ynyloxycarbonylethyl) -aniline.

70. N-β-cyanoethyl-N- (alyloxycarbonylethyl) -aniline.

71. N-β-hydroxyethyl-N- (alyloxycarbonylethyl) -aniline.

Example 72

40 parts of glacial acetic acid and 16.3 parts of 2-cyano-4-nitroaniline are added to 9.4 parts of 40% nitrosyl sulfuric acid, and 40 parts of glacial acetic acid are further added to this at 9.4 parts of 40% nitrosyl sulfate, keeping temperature constant at 10-15 degreeC.

After stirring for 2 hours, the obtained diazonium salt solution was kept at a constant temperature between 0 and 5 ° C., while maintaining 3-acetylamino-N-β-cyanoethyl-N- (3′-chloropropene-2′-yljade 35 parts of carbonylethyl) -aniline are slowly added to a solution of 60 parts of 50% acetic acid. After completion of the coupling, the reaction mixture was diluted with 500 parts of water, stirred for one hour, filtered, washed with acid and dried. The dye obtained has the following structural formula and dyes the polyester fiber in purple.

Example 73-91

According to the method described in Example 72, diazotized 2-cyano-4-nitroaniline is coupled with the coupling component of Examples 53-71. The dyes obtained dye the polyester fibers from red to purple.

Example 92-111

According to the method described in Example 52, however, the dye obtained by coupling 13.8 parts of 4-nitroaniline with the coupling component compound of Examples 52-71 instead of 17.2 parts of chloro-4-nitroaniline gave the polyester fiber a yellow color. 염색 stain from red to red.

Example 112

Dyes by coupling diazotized 2-bromo-4,6-dinitroaniline with N- (prop-2′-anioxycarbonylethyl) -α-naphthylamine in a similar manner as in Example 1 This dye dyes the polyester fibers with a reddish-blue indigo.

Example 113

In a similar manner as in Example 1, diazotized 2-bromo-4,6-dinitroaniline was combined with N- (3'-methoxybut-2'-ynyloxycarbonyl) -α-naphthylamino Coupling The obtained compound dyes the polyester fibers in a reddish indigo.

Example 114-122

According to the same method as in Example 1, instead of 2-bromo-4,6-dinitroaniline, a dye having a similar characteristic of dyeing in navy blue is obtained using the equivalent diazo components listed below.

2-cyano-4-nitro-6-bromoaniline,

2,4-dinitro-6-cyanoaniline,

2,4-dinitro-6-methylsulfonylaniline,

2,4-dinitro-6-methylsulfonylaniline,

2,6-dicyano-4-nitroaniline,

2-cyano-4-nitro-6-methylsulfonylaniline,

2-cyano-4-nitro-6-chloro or -urodoaniline,

2.5-dichloro-4,6-dinitroaniline.

Example 123-137

According to the same method as in Example 1, except for 5-acetylamino2-ethoxy-N- [3'-chloropropene- (2 ')-yloxycarbonylethyl] -aniline, To dye the polyester fiber indigo blue.

및

이다.Where X is

And

to be.

Table 1 below describes the dyes of the present invention and can be prepared analogously to the method described in Example 1.

Here, the general structural formula of the compound (dye) is as follows.

In the above, the definition of D, R ₁ , R ₅ , R ₆ , and the color dyed to the polyester fibers are shown in Table 1.

TABLE 1

Table 2 below describes dyes that can be prepared similarly to the method described in Example 1, and the general structural formulas of the dye compounds listed here are as follows.

Table 2 shows the definitions of D, R ₁ and X and the color that appears when the polyester fiber is dyed.

TABLE 2

[Application Example 1]

7 parts of the dye drawn by the method of Example 1 were mixed with 4 parts of sodium dinaphthylmethane disulfonate, 5 parts of sodium ethyl sulfate, and 5 parts of anhydrous sodium sulfate, and then ground for 48 hours to obtain fine powder. The suspension obtained by mixing 1 part of the obtained dye with a small amount of water is placed through a sieve in a dye container containing 2 parts of sodium lyryl sulfate in water.

100 parts of the cleaned polyester fiber were placed in a dye container at 40 to 50 ° C. (liquid ratio 1:40), and then 20 parts of chlorobenzene was added thereto, and the dye container was slowly heated to 100 ° C. Dyeing is effected effectively in 1-2 hours at 95-100 ° C. The dyed fibers are washed, soaped, washed again and then dried.

This deeply dyed navy blue has excellent fastness to light, washing, sublimation, heat, fixation and permanent compression.

Compounds obtained by the method of Example 2 to Example 197 can also be used to dye the pulley esters in the manner described above.

Claims (1)

A method of preparing a compound of formula (I) characterized by coupling a diazonium derivative of an amine of formula (II) with a compound of formula III.

In the above structural formula, D is a group of diazo component of benzene, pyrazole, thiophene, thiazole, isothiazole or thiadiazole type, K is 1,4-phenylene or unsubstituted 1,4-naphthalene and R ₁ Is hydrogen when K is unsubstituted 1,4-naphthylene or alkyl of (C ₁ -C ₄ ), and when K is 1,4-phenylene, R ₁ is hydrogen; Alkyl of (C ₁ -C ₄ ); Chlorine, bromine, vinylsulfonyl, hydroxy, cyano (C ₁ -C ₂ ) alkoxy, phenyl, acetyl, phenoxy, formyloxy, alkyl (C ₁ -C ₃ ) carbonyloxy, benzoyloxy, alkoxy ( C ₁ -C ₂ ) carbonyl, alkoxy (C ₁ -C ₂ ) carbonyloxy, alkyl (C ₁ -C ₂ ) alkylaminocarbonyl, di (C ₁ -C ₂ ) -alkylaminocarbonyl- or COOX (C ₁ -C ₄ ) alkyl monosubstituted with a hydroxy group and another substituted with one of chlorine, (= (C ₁ -C ₄ )) alkoxy, hydroxy, phenoxy or benzyloxy ( C ₁ -C ₄ ) alkyl and (C ₂ -C ₄ ) alkenyl; Or chloro- or bromo- (C ₃ -C ₄ ) alkel, R ₂ is straight or branched chain (C ₁ -C ₄ ) alkylene or —CH ₂ CH ₂ —O—CH ₂ CH ₂ — and X is

or

Wherein one of R ₃ and R ′ ₃ is hydrogen, the other is halogen, R ₄ is hydrogen or (C ₁ -C ₄ ) alkyl, and T ₁ is hydrogen; (C ₁ -C ₄₎ the by alkyl, chlorine or bromine mono-substituted (C ₁ -C ₄₎ alkyl, phenyl or chlorine, bromine, hydroxy, (C ₁ -C ₂₎ alkyl, (C ₁ -C ₂ ) substituted alkoxy or nitro to zero substitution at the selected two phenyl and T ₂ is hydrogen, (C ₁ -C ₄₎ alkyl, chlorine, bromine, or (C ₁ -C ₄₎ mono-substituted by alkoxy (C ₁ -C ₄ ) alkyl and U ₁ and U ₂ are each hydrogen or (C ₁ -C ₄ ) alkyl or U ₃ is hydrogen or

Or U ₁ and U ₂ together are attached to a carbon atom to form a cyclohexyl ring, U ₃ is hydrogen, U ₄ is hydrogen, (C ₁ -C ₄ ) alkyl or alkyl (C ₁ -C ₄ ) carbonyl .