KR960002658B1 - Improved organic-compounds and the preparation thereof - Google Patents

Abstract

No content.

Description

Improved Organic Compounds and Their Preparation Methods

The present invention relates to fiber-reactive phthalocyanine-monoazo compounds and to methods for their preparation. These compounds are suitable for use as fiber-reactive dyes in common dyeing and printing processes.

In particular, the present invention relates to a compound in which one of the tautomeric forms conforms to the following structural formula (I) in free acid or salt form or a mixture of compounds of the following structural formula (I).

, R₇은 수소, C_1-4알킬, C_5-6사이클로알킬, 페닐, 벤질, 페닐에틸 -또는 -COOH ;

는 비발색음이온; W는 -C_2-6알킬렌-, 모노히드록시-치환-C_3-6알킬렌-, -C_2-6알킬렌-사슬[이사슬은 -O-, -NR₃-,Wherein Pc is a phthalocyanine radical; Me is cobalt, copper or nickel; R ₁ and R ₂ are each hydrogen or C _1-6 alkyl; Each R ₃ is hydrogen, C _1-4 alkyl or C _2-4 hydroxyalkyl; R ₄ is hydrogen, halogen, hydroxy, C _1-4 alkoxy, C _1-4 alkyl, —COOH or —SO ₃ H; R ₅ is a halogen, —NH ₂ , aliphatic, cycloaliphatic, aromatic or heterocycloamino group; n is 0 or 1; R ₆ is hydrogen, -CONH ₂ or

, R ₇ is hydrogen, C _1-4 alkyl, C _5-6 cycloalkyl, phenyl, benzyl, phenylethyl-or -COOH;

Is nonchromic anion; W is -C _2-6 alkylene-, monohydroxy-substituted-C _3-6 alkylene-, -C _2-6 alkylene-chain [the chain is -O-, -NR _3- ,

를 형성하며 ; m는 0 또는 1 ; Y는 섬유-반응성기 ; a는 1-3의 수 ; b는 0-2의 수 ; c는 1-2의 수인데 ; 조건부로 a+b+c는 4를 초과하지 않는다.(Wherein -C _2-4 alkylene- is bonded to the nitrogen of the pyridone ring) or W is -C _2-4 alkylene with -NR ₃ -Y attached

To form; m is 0 or 1; Y is a fiber-reactive group; a is a number of 1-3; b is a number from 0-2; c is a number from 1 to 2; Conditionally a + b + c does not exceed 4.

c is a number from 1 to 2; Conditionally a + b + c does not exceed 4.

Unless stated otherwise, the alkyl or alkylene groups set forth in the specification are linear or branched. In any hydroxy-substituted alkyl or alkylene group attached to nitrogen, the hydroxy group is preferably bound to a carbon atom not directly attached to nitrogen.

In the compound of formula (I), Me is preferably copper or nickel, especially nickel.

Alkyl as R ₁ and R ₂ is preferably C _1-4 alkyl, more preferably C _1-2 alkyl.

Each of R ₁ and R ₂ is preferably R _1a and R _2a , wherein R _1a and R _2a are independently hydrogen or C _1-2 alkyl; Most preferably R ₁ and R ₂ are hydrogen.

Alkyl as R ₃ is preferably C _1-2 alkyl and hydroxy alkyl as R ₂ is preferably 2-hydroxyethyl.

Each R ₃ is preferably R _3c , more preferably R _3b , wherein R _3a is independently hydrogen, methyl, ethyl or 2-hydroxyethyl and R ₃ is independently hydrogen or methyl.

Halogen as R ₄ is preferably chlorine or bromine, especially chlorine. Alkyl or alkoxy as R ₄ preferably contains C _1-2 .

Each R ₄ is preferably R _4a , wherein each R _4a is independently hydrogen, chlorine, C _1-2 alkyl, C _1-2 alkoxy, —COOH, or —SO ₃ H.

Each R ₄ is better R _4b , where R _4b is independently hydrogen, methyl or —SO ₃ H. Each R ₄ is best R _4c , where R _4c is independently hydrogen or —SO ₃ H.

Halogen as R ₅ is preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine, most preferably chlorine.

Aliphatic, cycloaliphatic, aromatic or heterocycloamino groups as R ₅ preferably contain one or two groups selected from C _1-4 alkyl, C _5-6 cycloalkyl and phenyl, which are incompatible with the reactive dye art. Unsubstituted or substituted with up to 3 substituents, or R ₅ above contains up to 2 other heteroatoms such as N, O or S and may be substituted or substituted with saturated or partially unsaturated 5- or 6- The heterocycle of the member forms a ring. In any double substituted imino group, the two groups may be the same or different.

In any group as the R ₅ contains a substituted alkyl, such an alkyl group, hydroxy, C _1-4 alkoxy, -COOH, -SO ₃ H, unsubstituted phenyl, halogen, C _1-4 alkyl, C _1-4 To one or two substituents selected from phenyl, amino, -NHC _1-4 alkyl and-(N _1-4 alkyl) ₂ substituted by up to three substituents selected from alkoxy, -COOH, and -SO ₃ H C _1-4 alkyl substituted by is preferred.

In any amino group as R ₅ containing substituted phenyl groups, such phenyl groups are preferably 1- selected from halogen, more preferably chlorine, C _1-4 alkyl, C _1-4 alkoxy, -COOH, and -SO ₃ H. Substituted by three substituents.

In any amino group as R ₅ containing an unsubstituted or substituted C _5-6 cycloalkyl group, cyclohexyl which is capable of containing up to three C _1-4 alkyl groups is preferred.

Any heterocyclo amino group as R ₅ is preferably a saturated 6-membered ring which may contain one other 0 or N, and if substituted, such ring is preferably up to 3 C _1-4 alkyl groups, More preferably up to 3 methyl groups.

Each R ₅ is preferably R _5a , where each R _5a is independently fluorine, chlorine or —NR ₈ R ₉ , wherein each R ₈ and R ₉ is independently hydrogen, unsubstituted C _1-4 alkyl C _1-4 alkyl, monosubstituted with hydroxy, C _1-4 alkoxy, -COOH, -SO ₃ H, -NH ₂ , -NHC _1-4 alkyl or -N (C _1-4 alkyl) ₂ , non- Cyclic cyclohexyl, cyclohexyl substituted with 1-3 methyl groups, phenyl, or phenyl-C _1-4 alkyl, wherein the phenyl ring in the latter two groups is halogen, preferably chlorine, C _1-4 alkyl, C R ₈ and R ₉ together with nitrogen attached or unsubstituted or substituted with one or two groups selected from _1-4 alkoxy, -SO _c H and -COOH, are piperidine-, morpholine- or piperazine- Forming a ring, wherein the ring may contain up to three methyl groups.

More preferably, each R ₅ is R _5b , where each R _5b is independently fluorine, chlorine or —NR _8a R _9a , wherein R _8a and R _9a are each hydrogen, C _1-2 alkyl, hydroxy, CC _1-3 alkyl, phenyl or phenyl-C _1-2 alkyl- monosubstituted with -COOH or -SO ₂ H, the latter two phenyl rings being chlorine, methyl, methoxy, -SO _c H and- R _8a and R _9a together with nitrogen, substituted or unsubstituted or substituted with one or two substituents selected from COOH, form a piperidine-, morpholine-, or N-methylpiperazin-ring.

More preferably, each R ₅ is R _5c , where R _5c is each chlorine or —NR _8b R _9b , wherein each R _8b and R _9b is independently hydrogen, monohydroxy-substituted C _2-3 alkyl Or phenyl mono-substituted with methyl or sulfo.

Most preferably, each is R ₅ and R _5d , where R ₅₄ is independently chlorine or —NHR _9c , wherein R _9c is hydrogen or 2-hydroxy ethyl.

이다. 더욱 양호하게 R₆는 R_6b이며, 여기서 R_6b이며, 여기서 R_6b는 수소 또는 -CHNH₂이며, 가장 양호하게 R₆는 수소이다.R ₆ is preferably R _6a , wherein R _6a is hydrogen, -CONH ₂ or

to be. More preferably R ₆ is R _6b , where R _6b , where R _6b is hydrogen or —CHNH ₂ , most preferably R ₆ is hydrogen.

으로서의 어떠한 비-발색 음이온은 염기성 염료 화학분야에서 통상적인것, 예를들어 클로라이드, 브로마이드, 설페이트, 비설페이트, 메틸설페이트, 옥살레이트, 말레이트, 아세테이트, 락테이트, 숙신네이트, 타르트르에이트, 메탄 설포네이트 음이온등과 같은 유기 또는 무기 음이온일 수 있다. 그러나, 일반적으로, 그것은 반응매질이 음이온이므로, 클로라이드 또는 아세테이트 이온이 양호하다.

Any non-chromic anion as is common in the basic dye chemistry, for example chloride, bromide, sulfate, bisulfate, methylsulfate, oxalate, malate, acetate, lactate, succinate, tartrate, methane Organic or inorganic anions such as sulfonate anions and the like. Generally, however, chloride or acetate ions are preferred since the reaction medium is an anion.

Any alkyl as R ₇ is preferably methyl or ethyl, especially methyl. Cycloalkyl as R ₇ is preferably cyclohexyl.

R ₇ is preferably R _7a , wherein R _7a is methyl, ethyl, benzyl or cyclohexyl, most preferably R ₇ is methyl.

으로 중절될 수 있는 선형 폴리메틸린 사슬이 양호하다.Alkylene as W is -NR _3b -or

Preference is given to linear polymethylene chains which can be terminated with.

NR_3b-(CH₂)_q-, 3- 또는 4-위치에 유리결합을 가진

, 3- 또는 4-위치에 -(CH₂)_t-기를 가진

또는 -3 또는 4-위치에 유리결합을 가진

인데, p는 2, 3 또는 4이며, q는 각각 2 또는 3이고, t는 1 또는 2이고, 후자의 기-(CH₂)_q-는 피리돈고리의 질소에 부착되거나 ; 혹은 -NR₃-(Y)와 함께 W₁은

이다.W is W ₁ is good, and, in which W ₁ is _{- (CH 2) p -,} - (CH 2) q -NR 3b - (CH 2) q -, - (CH 2) q NR 3b

NR _3b- (CH ₂ ) _q -with a glass bond in the 3- or 4-position

, With-(CH ₂ ) _t -groups in 3- or 4-position

Or with a glass bond in the -3 or 4-position

P is 2, 3 or 4, q is 2 or 3, t is 1 or 2, and the latter group-(CH ₂ ) _q -is attached to the nitrogen of the pyridone ring; Or W ₁ with -NR _3- (Y)

to be.

이거나, 혹은 -NR₃-(Y)와 함께 W₂는

를 형성한다.More preferably, W is W ₂ , where W ₂ is-(CH ₂ ) _q -or

Or or together with -NR _3- (Y) W ₂

To form.

Most preferably W is W ₃ , where W ₃ is-(CH ₂ ) _q- .

The fiber-reactive group as Y is preferably Y _a , where Y _a is a group selected from the following structural formulas (a)-(i):

고리를 형성하거나, 혹은 두개의 -NR₃- 기중의 하나와 함께 B는

또는

를 형성하며 ; Y_f는 상기 (a), (b), (c), (d), (e), (i) 및 (j)의 기중의 하나이고 ; Y_g는

또는

(여기서, 후자의 2개의 기에서의 설포닐기는 각각 3- 또는 4-위치에 결합되며, Hal은 각각 염소 또는 브롬임)이며 ; Z는 분리될 수 있는 것이다.Wherein, in the latter four groups (i)-(1), each of -SO ₂ CH ₂ CH ₂ Z and -SO ₂ CH = CH ₂ is attached at the 3- or 4- position of the phenyl group; X ₁ is fluorine or —SO ₂ C _1-4 alkyl; X ₂ is C _1-4 alkyl or C _1-4 halogenalkyl; X ₃ is hydrogen or chlorine; X ₄ is an unsubstituted phenoxy wherein chlorine, hydroxy, C _1-4 alkoxy, phenyl group is substituted by one or two substituents selected from halogen, C _1-4 alkyl, C _1-4 alkoxy and —SO ₃ H Or -NR ₈ R ₉ ; X ₅ is -NR ₈ R ₉ ; X ₆ is fluorine, chlorine or —NR ₈ R ₉ , respectively; R ₃ , R ₈ and R ₉ are each as defined above; B is an aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic bridge member, or B with attached -NR _3-

Forming a ring, or together with one of two -NR ₃ -groups,

or

To form; Y _f is one of the groups of (a), (b), (c), (d), (e), (i) and (j); Y _g is

or

Wherein the sulfonyl groups in the latter two groups are each bonded in 3- or 4-position, and Hal is chlorine or bromine, respectively; Z can be separated.

X ₁ is preferably X _1a , wherein X _1a is fluorine or —SO ₂ CH ₃ .

X ₂ is preferably X _2a , wherein X _2a is methyl or —CH ₂ Cl.

X ₄ is preferably X _4a , wherein X _4a is chlorine, hydroxy, methoxy or —NR _8a R _9a ; More preferably X ₄ is X _4b , wherein X _4b is chlorine, hydroxy or —NR _8b R _9b ; Most preferably, X ₄ is X _4c , where X _4c is chlorine or —NHR _9c .

X ₅ is preferably X _5a , wherein X _5a is —NR _8a R _9a ; More preferably, X ₅ is X _5b , where X _5b is —NR _8a R _9a .

Each of X ₅ is an X _6a are preferably X _{6b, 6a} wherein X is independently fluorine independently, chlorine or -NR _8b R _9c.

B is preferably B ₁ , wherein B ₁ is —C _2-4 alkylene-, monohydroxy-substituted-C _3-4 alkylene,

고리를 형성하거나, 혹은 두개의 -NR₃-중 한개의 -NR₃-와 함께 B₁은

또는

를 형성한다.Wherein the cross-linking and-(CH ₂ ) _r -groups in the latter three phenyl groups are each at the 3- or 4-position, R is 1,2 or 3, R ₁₀ is hydrogen, chlorine, methyl, Methoxy, -SO ₃ H or -COOH; Or B ₁ with —NR ₃ — attached

Forming a ring, or together with one of two -NR ₃ --NR ₃ -B ₁

or

To form.

More preferably B is B ₂ , wherein B ₂ is —C _2-3 alkylene-, —CH ₂ CH (OH) CH ₂ —,

Wherein the crosslinks and-(CH ₂ ) _t -groups in the latter three phenyl groups are each in the 3- or 4-position and R _10a is hydrogen, methyl or -SO ₂ H; Or B ₂ together with the two —NR ₃ — attached form a piperazine ring.

Which can be separated Z is Z _a is in good standing and, Z is _a chlorine, -OSO ₃ H, -SSO ₃ H or -OCOC _1-4 alkyl.

(b) is preferably (b ₁ ), where (b ₁ ) is a group (b) in which X ₁ is X _1a and X ₂ is X _2a .

(d) is preferably (d ₁ ), wherein (d ₁ ) is a group (d) in which X ₄ is X _4a ; More preferably, (d) is (d ₂ ), where (d ₂ ) is a group (d) in which X ₄ is X _4b ; Most preferably, (d) is (d ₃ ), where (d ₃ ) is a group (d) where X ₄ is X _4c .

(e) is preferably (e ₁ ), wherein (e ₁ ) is a group (e) wherein X ₅ is X _5a ; More preferably, (e) is (e ₂ ), where (e ₂ ) is a group (e) which is X ₅ X _5b .

(f) is preferably the following formula (f ₁ ):

Wherein Y _f ′ is one of the groups of (a), (b ₁ ), (c), (d ₁ ) and (e ₁ ). More preferably, (f) is the following formula (f ₂ ).

Wherein Y _f "is one of the groups of (a), (c), (d ₂ ) and (e ₂ ). Most preferably Y _f " is (a).

(g) is preferably (g ₁ ), where (g ₁ ) is -CO-Y _g ', where Y _g ' is -CH = CH ₂ , -CH ₂ Cl,

Wherein each sulfonyl group in the latter two groups is bonded to the 3- or 4-position, respectively.

(i) is preferably (i ₁ ), where (i ₁ ) is a group in which X ₆ is X _6b , R ₃ is hydrogen, and Z is Z _a .

(j) is preferably (j ₁ ), where (j ₁ ) is a group (j) where X ₆ is X _6b and R ₃ is hydrogen.

(k) is preferably (k ₁ ), where (k ₁ ) is _a group (k) where Z is Z _a .

Y is preferably Y _b , more preferably Y _c , most preferably Y _e , where Y _b is (a), (b ₁ ), (c), (d ₁ ), (e ₁ ), (f ₁ ), (g ₁ ), (i ₁ ), (j ₁ ), (k ₁ ) and one of the groups of (1), Y _d is (a), (b ₁ ), (c), One of the groups of (d ₂ ), (e ₂ ) and (f ₂ ), Y _e is (a) or (b ₃ ).

n is preferably 0. a has a good number of 2-3, b has a good number of 0-1, and c has a good one.

Preferred compounds of the present invention include compounds of the following structural formula (Ia) in free acid or salt form.

R _4a of more preferable Compound (1) is each R _4b ; (2) R _6a is R _6b ; (3) R ₇ is R _7a ; (4) W ₁ is W ₂ , R _3a is R _3b is R _3b , and is a compound of formula (Ia).

More preferred are compounds of formula (Ib) below in free acid or salt form.

Wherein azo groups are bonded at the 3- or 4-position of the phenyl ring, m is 0 or 1, a ₁ is 2-3 and b ₁ is 0-1, where a ₁ + b ₁ is 3 Should not exceed

Most preferred compounds are those wherein (1) Y _b is Y _c ; (2) Y _b is Y _d ; (3) The compound of formula (Ib) wherein W ₂ is (1) or (2) which is W ₃ .

When the compound of formula (I) is in salt form, the cation associated with sulfo and carboxyl groups may be one of the non-chromic cations commonly used in the field of fiber-reactive dyes, provided that the corresponding salts are water soluble. It is not. Examples of such cations include alkali metal cations and substituted or unsubstituted ammonium cations such as lithium, sodium, potassium, mono-, di-, tri- and tetra-methyl ammonium, triethyl ammonium, mono-, di And tri-ethanol ammonium.

Preferred cations are alkali metal cations and ammonium and the best cations are sodium.

In the compounds of formula (I), the cations of sulfo and any carboxyl group may be the same or different, for example these cations may be in the form of salts in which the compounds of formula (I) are mixed. It may be a mixture of cations.

The present invention reacts a diazonium salt of the following formula (II) in the form of a free acid or salt with at least c mole of a compound of formula (III) present in one of the possible tautomeric forms, When Y _x in (III) is hydrogen, the present invention relates to a process for preparing the compound of formula (I) or a mixture thereof comprising reacting with at least c mole of compound Y-hal, where hal is fluorine, chlorine or bromine. .

The coupling reaction with the pyridone compound of formula III is suitably carried out by known methods at temperatures of 0-10 ° C. and in aqueous alkaline media.

It is preferable to use as a binding component a compound of the formula (III) wherein Y _x is hydrogen.

Similarly, the condensation reaction required to introduce the fiber-reactive group Y can be carried out according to known methods.

The compounds of formula (I) can be separated by known methods, for example by salting with alkali metal salts, followed by selective filtration and drying under vacuum and elevated temperature.

Depending on the reaction and separation conditions, the compound of formula (I) may be obtained in free acid form, preferably in salt form, or in mixed salt form containing one or more of the aforementioned cations. The compound may be converted from the salt form or a mixture of salt forms in the free acid form to the free acid form, or from one salt form to another by conventional methods.

Starting compounds of the formulas (II) and (III) are known, or may be prepared by known methods using known starting compounds. For example, phthalocyanine compounds common in the field of the compound phthalocyanine dyes of formula II can be prepared by sulfochlorination to react with _a suitable diamine and optionally NHR _a R _b amine.

Compounds of formula (I) and mixtures thereof are useful as fiber-reactive dyes for dyeing or printing hydroxy- or nitrogen-containing organic substrates. Preferred substrates are leather and fibrous materials which contain or consist of natural or synthetic polyamides, in particular natural or regenerated celluloses such as cotton, viscose and spanrayon and the like. The best substrates are woven materials containing or consisting of cotton fabrics.

Dyeing and printing at temperatures in the range of 30 ° C.-100 ° C. is carried out by known methods that are common in the field of fiber-reactive dyes. In order to prepare the compound of Structural Formula (I), it is preferable to use a vacuum dyeing method.

The compounds of the present invention may be compatible with other fiber-reactive dyes, and these dyes may be used on their own or have similar dyeing properties, such as general fastness, the ability to absorb fibers from dyeing vessels, and the like. It can be used in combination with the same class of suitable fiber-reactive dyes. The dyeing material obtained from such a binding mixture has excellent fastnesses and is compatible with the dyeing material obtained from one dye.

With regard to good combination power, the compound of formula (I) provides high absorption yield and color fastness yield. Some non-fastening dyes can be easily washed out of the substrate, and the dyeing and printing materials obtained exhibit high dry and wet, light fastness without degrading contact. Moreover, they exhibit excellent wet fastness to washing, water, seawater and moisture, and are also stable to the effects of oxidation, such as chloride, hypochlorite bleaching and peroxides, or perborates containing wash solution.

It is an advantage that dyeing by the compound of formula (I), which is commonly used at temperatures above 60 ° C., is not limited to these temperatures. Therefore, the same good effect can be obtained at 100 ° C. or 80 ° C. without loss of color fastness, and in fact dyeing materials of the same color strength can be obtained.

The following examples further illustrate the invention.

All parts and percentages in this example mean weight or volume percent and the temperature is 0 ° C.

Example 1

25.5 parts of a dye base was prepared according to a known method of sulfochlorinating nickel phthalocyanine and then reacting with 1,3-diaminobenzene-4-sulfonic acid containing about 2.5 sulfonic acids and one sulfonamido group per molecule. This dye base was stirred in 1.8 parts sodium nitrite solution in 150 parts water. The solution cooled to 0-2 ° C. was added dropwise to 100 parts ice water mixture and 12 parts 30% hydrochloric acid. Subsequently, 5.9 parts of 1- (3'-methylaminopropyl) -6-hydroxy-4-methylpyridone- (2) in 300 parts of ice water while maintaining the resulting diazonium salt suspension at a temperature of 0-5 ° C. It was added to the solution consisting of. During the coupling reaction, 30% sodium hydroxide solution was added to maintain the pH of the mixture at 9-9.5. A green solution (L ₁ ) was obtained, to which 5 parts of 5-chloro-2,4,6-trifluoropyrimidine were added and stirred at 0-5 ° C. for 3 hours. At the same time, sodium carbonate was added to maintain the pH at 8. After condensation was complete, the reaction mixture was salted with 45 parts of sodium chloride.

The precipitated dye was then filtered by suction and dried at 40 ° C. Dyes of the following structural formulas were obtained, dyeing light green cellulose materials, which showed good fastnesses:

Dyeing and printing materials for the area obtained by the common method have high fastness to light (dry and wet), in particular wet fastness. Furthermore, they are resistant to oxidative effects.

Example 2

According to the method of Example 1, instead of 5 parts of 5-chloro-2,4,6-trifluoropyrimidine, 5,6 parts of cyanuric chloride was used to condense into solution (L ₁ ). After 1 hour the reaction was complete and the dye was separated according to the method of Example 1. Thus, a dye of the following structural formula with a light green cellulose material was obtained:

Dyeing and printing materials for the area showed very good light and wet fastnesses.

Example 3

37 parts of the dye obtained according to the method of Example 2 were dissolved in 370 parts of water. Then, 200 parts of ice and 2 parts of monoethanolamine were added and the mixture was stirred at 0-5 ° C. for 1 hour. At the same time, about 3 parts of 30% sodium hydroxide solution was added to maintain the pH at 10. The dye was isolated according to the method of Example 1. A dye of the following structural formula was obtained, which was dyed a light green cellulose material:

The dyeing material having such a dye does not depend on the temperature, and since the effect can be almost the same at 80 ° C as at 98 ° C, dyeing materials having similar coloring strength can be prepared. Dyeing and printing materials for the area also show very good light and wet fastnesses and are stable against oxidative effects.

Example 4-15 / Table 1

Using suitable starting materials, the compounds of formula (I) can be prepared in a manner analogous to Example 1, listed in the table below. These compounds are consistent with the following structural formula (A):

The symbols defined below are used in Table 1 for Y:

The dyeing material and the printing material for the cotton cloth obtained with these compounds of Examples 4-15 have a bright green color. These materials exhibit good wet fastnesses.

TABLE 1

Compound of Structural Formula (A)

Example 16-116 / Table 2-4

In a similar manner to Examples 1,2 or 3, using appropriate starting compounds, compounds of formula (I) were prepared. This compound is consistent with formula (B).

In the above formulas, symbols are defined in Tables 2-4.

Example 16-48 / Table 2

For these compounds listed in Table 2, n is zero. These compounds dye cellulosic materials of light green color. These dyeing materials and printing materials exhibit excellent fastness such as light and wet fastness.

TABLE 2a

compound of formula (B) with n = 0

TABLE 2b

Example 49-71 Table 3

For the compounds listed in Table 3, n is 1 and R ₂ is -SO ₃ H. These compounds dye light green cellulosic materials, and their dyeing and printing materials exhibit good fastnesses.

TABLE 3

23n = 1 and R is -SO ₃ H. A compound of formula

Example 72-116 Table / (4)

In the compounds listed in Table 4, R ₆ is hydrogen. The symbol Y ₄ -Y ₁₅ in Y is defined as follows.

TABLE 4a

A compound of formula (B) wherein R ₆ is hydrogen

TABLE 4b

TABLE 4c

The compounds of Examples 72-116 dye the light green cellulose material. These dyeing and printing materials exhibit excellent light and wet fastnesses.

According to the above-mentioned method, the dyes of Examples 1-116 are obtained in the form of sodium salts. Furthermore, depending on the reaction / separation conditions or by reaction of the sodium salts according to known methods these dyes are obtained in free acid form or in the form of other salts, for example in the form of salts containing one or more cations mentioned in the text above. Lose.

Application of the compound of the present invention is described in the following Examples.

Application Example A

0.3 parts of the dye of Example 1 are dissolved in 300 parts of demineralized water and 15 parts of Glauber's salt (calcined) are added. The dye container is heated to 40 ° C. and then 10 parts cotton fibers (bleached) are added. After 30 minutes at 40 ° C., 6 parts of sodium carbonate (calcined) are added to the dye container in small amounts in amounts of 0.2, 0.6, 1.2 and finally 4.0 parts every 10 minutes. During the addition of sodium carbonate, the temperature is maintained at 40 ° C., and then the dyeing is effectively carried out at 40 ° C. for 1 and a half hours.

The dyed fibers are then rinsed with circulating cold water for 3 minutes and then with hotter circulating water for 3 minutes. The dyeing material is washed at boiling point for 15 minutes in 500 parts of demineralized water in the presence of commercially available 0.25 parts of anionic-active detergent. After rinsing with hot circulating water (3 minutes), centrifugation, the dyeing material is dried to about 70 ° C. in a cabinet drier. A bright green cotton dyeing is obtained, which shows good fastness, especially to light.

Application Example B

The method of Application Example A was modified and only the calcined 2 parts sodium carbonate was added little by little, instead of the total 6 parts sodium carbonate added little by little. Raise to 60 ° C. at the initial 40 ° C., and perform further dyeing for 1 hour. Otherwise, the method of application example A is used. A bright green cotton dyeing material is obtained, which shows very good light fastness.

Application Example C

20 parts salt of Glauber (calcined), 2.5 parts sodium carbonate (calcined), and 1 part sodium salt of 1-nitrobenzene-3-sulfonic acid, 50 parts mercerized cotton fibers consisting of 100 parts water To the dye container. The vessel is heated to 40 ° C. and then 100 parts of the dye of Example 3 are added. The temperature is raised to 98 ° C. within 45 minutes, during which time 20 parts of Glauber's salt (calcined) are added after 15 minutes and 20 parts of Glauber's salt (calcined) are added after 15 minutes. At the end of this time, 7.5 parts of sodium carbonate (calcined) are added. Staining is carried out at boiling point for 45-60 minutes, then the dyed fibers are removed from the liquid, rinsed with hot circulating water and then washed at the boiling point according to the method of application example A. After rinsing and drying a bright green cotton dyeing material was obtained with good light and wet fastnesses.

Application Example D

2.5 parts of the dye of Example 3 were dissolved in 2000 parts of water, 100 parts of cotton fiber were added, and the temperature of the dye container was raised to 80 ° C. within 10 minutes. 100 parts of Glauber's salt (calcined) are added and after 30 minutes 20 parts of sodium carbonate (calcined) are added. The dyeing is carried out at 80 ° C. for 1 hour, and then the dyed fibers are rinsed with circulating cooling water and then again with hot water and washed to boiling point according to the method of Application Example A.

After rinsing and drying, a bright green cotton dyeing material with good fastness is obtained.

Similarly, the dyes of Examples 2 and 4-116 or mixtures of these dyes are used to dye cotton wool according to the methods of Application Examples A-D.

Application Example E

A total of 100 parts of a printing paste consisting of 40 parts of the dye of Example 1, 100 parts of urea, 350 parts of water, 500 parts of 4% sodium alginate thickener and 10 parts of sodium bicarbonate was added to the cotton fiber according to a common printing method. It was.

The printing fibers are dried and then fixed with steam at 102-104 ° C. for 4-8 minutes. It is rinsed with cool water and rinsed with hot water again, washed and dried at boiling point according to the method of application example A. Generally bright green printing materials are obtained with good fastnesses.

Similarly, the dyes of Example 2-116 or mixtures thereof are used to print cotton wool according to the method of Application Example E.

Claims (12)

A compound of formula (I) or a mixture thereof, in free acid or salt form, present in one of the tautomeric forms:

Wherein Pc is a phthalocyanine radical; Me is cobalt, copper or nickel; R ₁ and R ₂ are each hydrogen or C _1-6 alkyl; Each R ₃ is hydrogen, C _1-4 alkyl or C _2-4 hydroxyalkyl; Each R ₄ is hydrogen, halogen, hydroxy, C _1-4 alkoxy, C _1-4 alkyl, —COOH or —SO ₃ HR ₅ is halogen, —NH ₂ , an aliphatic, cycloaliphatic, aromatic or heterocycloamino group; n is 0 or 1; R ₆ is small, -CONH ₂ or

; R ₇ is hydrogen, C _1-4 alkyl, C _5-6 cycloalkyl, phenyl, benzyl, phenylethyl-or -COOH;

Is non-chromic anion; W is -C _2-6 alkylene-, monohydroxy-substituted-C _3-6 alkylene-, -C _2-6 alkylene-chain [the chain is -O-, -NR _3- , or

Aborted by]

,

Alkylene- or-C _2-4 alkylene

(Wherein the latter group -C _2-4 alkylene- is defective in the nitrogen of the pyridone ring), or W is -C _2-4 alkylene with -NR ₃ -Y attached

To form; m is 0 or 1; Y is a fiber-reactive group; a is a number of 1-3; b is a number from 0-2; c is a number from 1 to 2; Conditionally a + b + c does not exceed 4. The compound of claim 1, wherein Me is copper or nickel. The compound of claim 2, wherein R ₁ and R ₂ are each hydrogen. The compound of claim 2, which is hydrogen or —SO ₃ H of each R ₄ . The compound of claim 2, wherein R ₆ is hydrogen or —CONH ₂ . A compound according to claim 1 in accordance with the following structural formula (Ib) in free acid or salt form:

Wherein the azo group is bonded to the 3- or 4-position of the phenyl ring; m is 0 or 1; a ₁ is a number of 2-3; b1 is a number 0-1, where a ₁ + b ₁ must not exceed 3; Each R _3b is hydrogen or methyl; W ₂ is-(CH ₂ ) _q -or

Inde, where each q is 2 or 3, R _5d represents a chlorine, -NH ₂ or -NHCH ₂ CH ₂ OH, or or, -NR _3b - (Y _b) and W ₂ together are

And; Y _b is the following (a), (b ₁ ), (c), (d ₁ ), (e ₁ ), (f ₁ ), (g ₁ ), (i ₁ ), (j ₁ ), (k ₁ ) and (1) are one of the groups:

Wherein, (i _{1), (1} j), (k ₁₎ and (1) each group of -SO ₂ CH ₂ CH ₂ Za, and -SO ₂ CH = CH ₂ is a phenyl group or in the 3-4- Attached in position; X _1a is fluorine or —SO ₂ CH ₃ ; X _2a is methyl or —CH ₂ Cl; X ₃ is hydrogen or chlorine; X _4a is chlorine, hydroxy, methoxy, or —NR _8a R _9a , wherein R _8a and R _9a are each monosubstituted with hydrogen, C _1-2 alkyl, hydroxy, —COOH or —SO ₃ H C _1-3 alkyl, phenyl or phenyl-C _1-2 alkyl wherein the latter two phenyl rings are substituted with one or two substituents selected from chlorine, methyl, methoxy, -SO ₃ H and -COOH or R _8a and R _9a together with unsubstituted or attached nitrogen form a piperidine-, morpholine-, piperazine-, or N-methylpiperazin- ring; X _5a is —NR _8a R _9a ; X _6a is fluorine, chlorine or —NR _8a R _9a ; B ₁ is —C _2-4 alkylene-, monohydroxy substituted —C _3-4 alkylene-

Wherein the crosslinking and — (CH ₂ ) _r — groups in the latter three phenyl groups are each 3- or 4-position, r is 1,2 or 3, R _{10 is} hydrogen, chlorine, methyl, methoxy, -SO ₃ H or -COOH; Or B ₁ together with the two —NR _3b — attached

Forming a ring, or together with one of two -NR _3b -NR _3b , B ₁

To form; Y _f ′ is one of the groups of (a), (b ₁ ), (c), (d ₁ ) and (e ₁ );

or

Wherein the sulfonyl group in the latter two groups is bonded at the 3- or 4-position; X _6b is chlorine or —NR _8b R _9b , wherein R _8b and R _9b are each hydrogen, monohydroxy-substituted-C _2-3 alkyl, or phenyl monosubstituted with methyl or sulfo; Z _a is chlorine, —OSO ₃ H, —SSO ₃ H or —OCOC _1-4 alkyl. The method of claim 6, wherein, W ₂ is - (CH _{2) q} of the W _3, and; Y _b is a compound which is Y _d of the group of (a) or (d ₃ ) below,

Wherein X _4c is chlorine or —NHR _9c and R _9c is hydrogen or 2-hydroxyethyl. The diazonium salt of the compound of formula (II), which is in the form of a free acid or salt, is reacted with at least c moles of the compound of formula (III) present in one of the possible tautomeric forms, Of compounds of formula (I) or mixtures thereof as defined in claim 1 comprising reacting with at least c moles of compound Y-hal, wherein hal is fluorine, chlorine or bromine when Y _x is hydrogen Way:

All codes except the above formula, Y _x are as defined in claim 1, Y _x is hydrogen or a fiber-reactive group is a Y. The method of claim 8 comprising reacting a compound of formula III wherein Y _x is hydrogen. A method of dyeing or printing a hydroxy group- or nitrogen-containing organic substrate comprising applying to the substrate a compound of formula (I) or a mixture thereof as defined in claim 1 as a dyeing or printing agent. The method of claim 10 wherein the substrate is a fibrous material or leather containing or consisting of natural or regenerated cellulose. The method of claim 11, wherein the substrate is a fabric containing or consisting of cotton.