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GB2034733A - Azo dyes - Google Patents

Azo dyes Download PDF

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Publication number
GB2034733A
GB2034733A GB7931821A GB7931821A GB2034733A GB 2034733 A GB2034733 A GB 2034733A GB 7931821 A GB7931821 A GB 7931821A GB 7931821 A GB7931821 A GB 7931821A GB 2034733 A GB2034733 A GB 2034733A
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Prior art keywords
hydrogen
dye
unsubstituted
substituted
chlorine
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GB7931821A
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BASF SE
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BASF SE
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00Monoazo dyes prepared by diazotising and coupling
    • C09B29/34Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3617Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
    • C09B29/3621Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
    • C09B29/3639Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more amino groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • C09B29/0011Monoazo dyes prepared by diazotising and coupling from diazotized anilines from diazotized anilines directly substituted by a heterocyclic ring (not condensed)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Coloring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Novel azo dyes have the general formula <IMAGE> where A is cyano or carbamyl, R is hydrogen, alkyl or phenyl, R<1> is hydrogen, bromine, chlorine or nitro, X is a sulfonic acid ester group or unsubstituted or substituted sulfamyl, R<3> is hydrogen or a C1-C8-alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, C1-C8- alkoxy or phenoxy, or is benzyl, phenylethyl or cyclohexyl, or is unsubstituted or chlorine-, bromine-, nitro-, methyl-, ethyl-, phenoxy- or di-C1-C4-alkylamino-substituted phenyl, naphthyl, pyridyl, thienyl or furyl, the substituents B<1> independently of one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic, heterocyclic or acyl radical, and B<2> is hydrogen or an aliphatic radical. The dyes according to the invention are outstandingly suitable for dyeing polyesters, cellulosic fabrics, leather, coating compositions and organic solvents.

Description

SPECIFICATION Azo dyes The present invention relates to azo dyes. The azo dyes of the invention are compounds of the general formula I
where A is cyano or carbamyl, R is hydrogen, alkyl or phenyl, R1 is hydrogen, bromine, chlorine or nitro, X is a sulfonic acid ester group or unsubstituted or substituted sulfamyl, R3 is hydrogen or a C1-C8-alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, C1-C8-alkoxy or phenoxy, or is benzyl, phenylethyl or cyclohexyl, or is unsubstituted or chlorine-, bromine-, nitro-, methyl-, ethyl-, phenoxy- or di-C1-C4- alkylamino-substituted phenyl, naphthyl, pyridyl, thienyl or furyl, the substituents B' independently of one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic, heterocyclic or acyl radical and B2 is hydrogen or an aliphatic radical.
Examples of alkyl R are radicals of 1 to 6 carbon atoms, particularly methyl, ethyl, propyl, butyl and pentyl.
Examples of radicals X are sulfonic acid aryl ester groups, and sulfamyl which is monosubstituted or disubstituted by C1-C8-alkyl, by alkoxy-, polyalkoxy-, phenoxy-, phenoxyalkoxy- or benzyloxysubstituted C2-C3-alkyl, by phenyl-C1-C4-alkyl, by cyclohexyl or by unsubstituted or methyl-, ethyl-, methoxy-, ethoxy-, chlorine- or bromine-substituted phenyl.
Specific examples of radicals X are: SO2OT; T=C6H5, C6H4Cl, C6G4CH3, C6H4OCH3 or C6H3(CH3)2 SO2T1; T' = NHCH3, NHC2H5, NHC3H7, NHC4Hg, NHC6H,3, NHC8H17,
NHC2H4OCH3, NHC2H4OC2H5, NHC2H4OC4H9, NHC2H40C2H40CH3, NHC2H4OC2H4O04H9, NH(CH2)3, NH(CH2)3OCH3, NH(CH2)3OC2H4OC2H5, NH(CH2)3OC9H7, NH(CH2)3OC4H9, NH(CH3)2OC2H4OCH3, NH(CH2)3OC2H4OC4H9, NH(CH2)3OC2H4OC6H5, NH(CH2)3OC2H4OCH2C6H5, the corresponding disubstituted radicals, in which the radicals T1 may differ from one another, and NHCH2C6Hs, NHC2H4C6Hs,
NHC6H11, NHC6Hs, NHC6H4CH3, NHC6H4C2H5, NHC6H4OCH3, NHC6H4CI, NHC6H3(CH3)2,
Preferred radicals X are the sulfonic acid ester groups and di-C1-C4-aikyl-substituted or monoaryl-substituted sulfamyl.
Radicals B1 are for example, independently of one another, hydrogen, methyl, C2-C8-alkyl which may or may not be interrupted by ether oxygen and is unsubstituted or substituted by hydroxyl, C1-C8- alkoxy, benzyloxy, p-phenylethoxy, phenoxy, tolyloxy, cyclohexyloxy or cyano, C9-C18-alkyl, C5-C8- cycloalkyl, hydroxycyclohexyl, p-hydroxyethoxycyclohexyl, C7-C12-polycycloalkyl, hydroxynorbornyl, hydroxymethylnorbornyl, hydroxyethylnorbornyl, ch loromethylnorbornyl, phenylalkyl or tolylalkyl, where alkyl is of 1 to 4 carbon atoms, unsubstituted or chlorine-, hydroxy-, methoxy-, ethoxy-, methyl-, ethylor hydroxyethoxy-substituted phenyl, allyl, pyrrolidonylalkyl, where alkyl is of 2, 3, 4 or 6 carbon atoms, carboxyalkyl, where alkyl is of 2 to 5 carbon atoms,
Examples of B2 are the same as the aliphatic radicals mentioned for B1, and examples of R3, to the extent that the general definitions coincide, are also the same as for B1.
Specific examples of radicals B' and BZ, to the extent that they fall under the general definition, are, in addition to those already mentioned, 1. unsubstituted or substituted alkyl radicals: CH3, C2H5, n- or i-C3H7, n- or i-C4H9, C6H13,
(CH2)2O(CH2)2OH, (CH2)30(CH2)4OH, (CH2)3OC2H4OH, (CH2)2CN, (CH2)5CN, (CH2)6CN, (CH2),CN, (CH2)2O(CH2)2CN, (CH2)3O(CH2)2CN, (CH2)20(CH2)20(CH2)2CN, (CH2)3OC2H40CH3, (CH2)3OC2H40C2H5, (CH2)3O(CH2)6OH, (CH2)3OC2H4OCH(CH3)2, (CH2)3OC2H4OC4H9, (CH2)3OC2H4OCH2C6H5, (C H2)3OC2H4OC2H4C6H5,
the corresponding radicals in which the group
occurs twice or three times, CH2CH2OCH3, CH2CH2OC2H5, CH2CH2OC3H7, CH2CH2OC4H9, CH2CH2OC6H5, (CH2)3OCH3, (CH2)3OC2H5,
(CH2)3OC8H13, (CH2)3OC8H17, (CH2)3O-, (CH2)3OCH2C6H5, (CH2)3OC2H4C6H5, (CH2)3OC6H5,
2. unsubstituted or substituted cycloalkyl and polycycloalkyl radicals:
3. aralkyl radicals:
as well as the corresponding radicals containing C6H4CH3 in place of C6Hs; 4. unsubstituted or substituted phenyl radicals: C6H5, C6H4CH3, C6H3(CH3)2, C6H4OCH3, C6H40C2Hs, C6H40H,
5.
CH2CH-CH2, (CH2)2COOH, (CH2)5COOH and
where n is 2, 3,4 or 6, C2H4OCOCH3, C2H4OCHO, C2H4OCOCH3, (C2H4O)2COCH3, (C2H4O)2CHO, (CH2)3OCOCH3, (CH2)3OCHO, and C2H40COC2H4COOH.
Examples of preferred substituents B' and 82 are hydrogen, CH3, C2H5, n- or i-C3H7, n- or i-C4H9, C6H13, CH2CH2OH, (CH2)3OH,
(CH2)2O(CH2)2OH, (CH2)3O(CH2)2OH, (CH2)3O(CH2)4OH,
CH2CH2OCH3, CH2CH2OC2H5, CH2CH2OC4H9, (CH2)3OCH3, (CH2)3OC2H5, (CH2)3OC3H7, (CH2)3OC4H9,
Examples of radicals
are pyrrolidino, piperidino, morpholino and N-methylpiperazino.
Preferred diazo components are those set out in Table 1.
TABLE 1
Formula T R' R3 1 -N(C2H5)2 H 06H5 2 -N(C4H9) H C6H5 3 \ H -CH,-O-CH, A 4 -N O H -CH2-CH2-0-CH2-C6H5 P 5 -Ne H C6H5 6 -NOcH3 H C6Hs 7 -N-C1 H C6Hs 8 OC6H5 H CH5 9 3 H 06H3 10 -N(C,H,) Br 11 " Br CH2CH24C3H7 12 -N(C4H9) Br QH TABLE 1 (Continued) Formula T Rl R3 13 -N(C4H9) Br -CH2-CH2O-C3H7 14 -N(C2H,) Br 15 H H 16 OC6Hs H On cellulose fibers, natural polyamides, nylons, polyesters and other synthetic fibers, the dyes of the formula I give yellow to red dyeings having very good lightfastness, fastness to thermofixing and wetfastness. The deep colors and clear hues achievable with many of the dyes deserve particular mention. The dyes of the formula I are particularly suitable for the process described in German Patent 1,81 1,796, i.e. a process in which cellulosic fibers are contacted with water and an oxyethylene or oxypropylene compound to swell the fibers and, whilst the fibers are still swollen, with a dye according to the invention. Some of them may also be used as solvent dyes, for example for dyeing coating compositions, solvents or leather.
Dyes of particular industrial importance are those of the formula la
where R4 is hydrogen or chlorine, Re is methyl, C1-C4-alkoxyethyl, phenoxyethyl, phenyl or pyridyl and A, Bt, B2, X and R have the above meanings.
Preferably R is hydrogen or methyl and B2 is hydrogen. Another preferred combination is where R is H and A is CONY,.
The preferred meanings of B' are as stated earlier.
A dye of the formula I may be prepared by reacting a diazonium compound of an amine of the formula
with a coupling component of the formula
AR, R1, X, R3, B1 and B2 having the above meanings. The diazotization and coupling may be carried out by conventional methods.
In the Examples which follow, parts and percentages are by weight, unless stated otherwise.
EXAMPLE 1 32 parts of 40% strength nitrosylsulfuric acid are added to a solution of 30 parts of the compound of the formula1 in Table 1 in 1,500 parts by volume of glacial acetic acid and 200 parts of propionic acid at 0--50C, and the mixture is stirred at this temperature for 2 hours. Excess nitrosylsulfuric acid is then destroyed with urea. A solution of 27 parts of 2,6-bis-(2'-methoxyethylamino)-3-cyano-4methylpyridine in 500 parts of glacial acetic acid is then added to the diazotization mixture at 0--50C, followed by a total of 50 parts of anhydrous sodium acetate added gradually. After completion of coupling, the dye which has formed is filtered off, washed with ethanol and then with water, and dried at 1000. An orange powder is obtained, which gives an orange solution in N-methylpyrrolidone.On cotton or polyester or cotton/polyester union fabrics, this dye, used by the process described in German Patent 1,81 1,796, gives strong orange hues with excellent fastness characteristics.
The following dyes may be obtained by similar methods: Coupling component
Uiazo component Example from Table 1 R' R Hue 2 2 -(CH2)2-O-CH3 -(CH2)2-O-CH3 orange 3 4 ,, " orange 4 5 " p, orange 5 8 p, " reddish orange 6 12 p, " orange 7 1 (CHa)aOCH3 -( CH2)3O-CH orange 8 2 " p, orange 9 9 4 ,, pp orange 10 5 p, " orange 11 8 pp " bright red 12 9 ,1 13 1 -C4H, -C4H9 orange 14 2 p, 15 3 pp pp 16 5 pp " pp 17 6 p, pp p, 18 7 pp " "pp 19 8 " " bright red 20 9 p, pp 21 -CH2-CH2 -CH2-CH2 < ) , orange 22 1 -CH2-CH2-O-CH, H golden yellow 23 2 pp H p, 24 4 H H 25 1 -(CH2)J-O-(CH2)2-O- H yellowish orange Coupling component
Diazo component Example from Table 1 R1 R2 Hue 26 2 (CH2)3-o-(cH2)2-o < ) H yellowish orange 27 4 pp H orange 28 5 p, H p, 29 7 pp H pp 30 8 pp H o, 31 2 -(CH,),-O-CH, -(CH2)30-(CH2)2'0 32 8 pp " bright red 33 3 " " orange The following compounds are particularly suitable for use as solvent dyes: Coupling component Diazo component (as for Examples 2-33) Example of Table 1 R1 @@ R2 Hue 34 18 -(CH2)3-O-(CH2)4-OH yellowish orange 35 11 p, golden yellow 36 12 p, yellowish orange 37 13 " golden yellow 38 14 " golden yellow 39 15 " yellowish orange 40 16 " reddish orange
Example n X Y R1 = R2 Hue 41 3 NHC6H5 Br C2H4OH orange 42 3 " " C2H4OCH3 " 43 3 " " C3H6OCH3 " 44 3 " " C3H6OH " 45 3 " " C2H4OC2H4OH " 46 3 " " (CH2)3O(CH2)4OH " 47 4 " " C2H4OH " 48 4 " " C2H4OCH3 " 49 4 " " C2H4OC2H4OH " 50 4 " " C3H6OCH3 " 51 4 " Cl " " 52 4 " " C2H4OC2H4OH " 53 3 " " " " 54 3 OC6H5 " " " 55 3 " Br " " 56 3 " " C2H4OH " 57 3 " " C2H4OCH3 " 58 3 " H " " 59 3 " H C2H4OC2H4OH " 60 3 " Br (CH2)3O(CH2)4OH " 61 3 " " C3H2OCH3 " 62 3 " " C3H6OH " 63 4 " " C2H4OH " 64 4 " " C2H4OCH3 " 65 4 " " C2H4OC2H4OH " 66 4 " " " "

Claims (8)

1. An azo dye of the general formula
where A is cyano or carbamyl, R is hydrogen, alkyl or phenyl R1 is hydrogen, bromine, chlorine or nitro, X is a sulfonic acid ester group or unsubstituted or substituted sulfamyl, R3 is hydrogen or a C,--C,-alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, C1-C8-alkoxy or phenoxy, or is benzyl, phenylethyl or cyclohexyl, or is unsubstituted or chlorine-, bromine-, nitro-, methyl-, ethyl-, phenoxy- or di-C1-C4- alkylamino-substituted phenyl, naphthyl, pyridyl, thienyl or furyl, the substituents B1 independently of one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic, heterocyclic or acyl radical and B2 is hydrogen or an aliphatic radical.
2. A dye as claimed in claim 1, wherein R, X, R3, B1 and B2 denote radicals individually identified hereinbefore as examples thereof.
3. A dye as claimed in claim 1, of the formula
where R4 is hydrogen or chlorine, R6 is methyl, C1-C4-alkoxyethyl, phenoxyethyl, phenyl or pyridyl and A, B', B2, X and R have the meanings given in claim 1.
4. A dye as claimed in claim 1 and identified in any of the foregoing Examples 1 to 66.
5. A process for the preparation of a dye as claimed in claim 1, wherein a diazonium compound of an amine of the formula
is reacted with a coupling component of the formula
A, R, R1, X, R3, B1 and B2 having the meanings given in claim 1.
6. A process as claimed in claim 5, wherein a diazonium compound of an amine listed in Table 1 hereinbefore is used.
7. A dye formulation for dyeing natural and synthetic fibers, which contains a dye as claimed in any of claims 1 to 4 or prepared by a process as claimed in claim 5 or 6 together with one or more conventional constituents for dye formulations for such purposes.
8. A process for the mass-dyeing of thermoplastics material or for dyeing leather, coating compositions or organic solvents wherein a dye as claimed in any of claims 1 to 4 or prepared by a process as claimed in claim 5 or 6 is used.
GB7931821A 1978-09-14 1979-09-13 Azo dyes Withdrawn GB2034733A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19782839905 DE2839905A1 (en) 1978-09-14 1978-09-14 AZO DYES

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GB2034733A true GB2034733A (en) 1980-06-11

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GB7931821A Withdrawn GB2034733A (en) 1978-09-14 1979-09-13 Azo dyes

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JP (1) JPS5540783A (en)
DE (1) DE2839905A1 (en)
FR (1) FR2436163A2 (en)
GB (1) GB2034733A (en)
IT (1) IT1123565B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD377875S (en) 1994-10-20 1997-02-11 President Office Furniture Ltd. Leg support

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH611324A5 (en) * 1974-04-09 1979-05-31 Basf Ag

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD377875S (en) 1994-10-20 1997-02-11 President Office Furniture Ltd. Leg support

Also Published As

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FR2436163A2 (en) 1980-04-11
JPS5540783A (en) 1980-03-22
IT7925550A0 (en) 1979-09-07
IT1123565B (en) 1986-04-30
DE2839905A1 (en) 1980-04-03

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