WO1995028447A1 - Disperse dyes derived from hindered indoline couplers - Google Patents

Disperse dyes derived from hindered indoline couplers Download PDF

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Publication number
WO1995028447A1
WO1995028447A1 PCT/GB1995/000675 GB9500675W WO9528447A1 WO 1995028447 A1 WO1995028447 A1 WO 1995028447A1 GB 9500675 W GB9500675 W GB 9500675W WO 9528447 A1 WO9528447 A1 WO 9528447A1
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Prior art keywords
formula
alkyl
group
optionally substituted
aryl
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PCT/GB1995/000675
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French (fr)
Inventor
Mark Robert James
Roy Bradbury
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Zeneca Limited
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Priority to AU19569/95A priority Critical patent/AU1956995A/en
Publication of WO1995028447A1 publication Critical patent/WO1995028447A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3608—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered heterocyclic ring with only one nitrogen as heteroatom
    • C09B29/3613—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered heterocyclic ring with only one nitrogen as heteroatom from an indole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/12—Disazo dyes from other coupling components "C"
    • C09B31/14—Heterocyclic components
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B53/00—Quinone imides
    • C09B53/02—Indamines; Indophenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C09B55/009—Azomethine dyes, the C-atom of the group -C=N- being part of a ring (Image)

Definitions

  • the alkyl group represented by R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 is preferably C 1-20 -alkyl, more preferably and especially C._ B - alkyl.
  • the cycloalkyl group represented by R and R 1 is preferably C 4 _ ⁇ - cycloalkyl, more preferably cyclohexyl.
  • A is preferably a group of Formula (2) , Formula (3) , Formula (4) , Formula (9) or Formula (10) , more preferably a group of Formula (2) or Formula (4) .
  • R 1 is preferably C ⁇ e -alkyl, more preferably an ⁇ -branched C 3 .
  • e -alkyl or a straight chain C 1-B -alkyl and especially 1-methylhexyl, n-heptyl, n-butyl, i ⁇ obutyl R 2 and R 3 are preferably Ci- e -alk l, more preferably C ⁇ -alkyl and especially methyl,
  • R 4 is preferably -H, C 1- ⁇ -alkyl, -NHCOCi.
  • Dyes of Formula (1) in which A is a group of Formula (6) and R 13 is H may be prepared by condensation of a co ⁇ pound of Formula (1) in which A is -CHO with an active methylene co ⁇ pound such as alonitrile or an alkylcyanoacetate such as ethylcyanoacetate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

A disperse dye of formula (1), in which R1 is alkyl, cycloalkyl, aryl, alkenyl or aralkyl each of which may be optionally substituted; R?2 and R3¿ each independently is optionally substituted alkyl; R4 is -H, -OH or alkyl, alkoxy, - NHCOalkyl, -NHCOaryl, -NHSO¿2?alkyl, -NHSO2aryl each of which may be optionally substituted; Z is a direct link, oxygen or -N-R?5¿ in which R5 is -H, otpionally substituted alkyl or optionally substituted aryl; A is a group as defined in claim 1. The present hindered indoline dyes are useful for the coloration of textile materials, for use in coloured toners, in inks and as dyes for dye diffusion thermal transfer printing.

Description

DISPERSE DYES DERIVED FROM HINDERED INDOLINE COUPLERS
This invention relates to disperse dyes particularly to disperse dyes having hindered indoline couplers, to mixtures comprising such dyes, to the use of such dyes for the coloration of textile materials, to the use of such dyes in coloured toners, in inks, in dye diffusion thermal transfer printing and to certain indoline couplers.
According to the present invention there is provided a disperse dye of Formula (1) :
Figure imgf000003_0001
Formula (1 ) in which
R1 is alkyl, cycloalkyl, aryl, alkenyl or aralkyl each of which may be optionally substituted;
R2 and R3 each independently is optionally substituted alkyl; R4 is -H, -OH or alkyl, alkoxy, -NHCOalkyl, -NHCOaryl, -
NHSO;alkyl, -NHS02aryl each of which may be optionally substituted; Z is a direct link, oxygen or -N-R5 in which R5 is -H, optionally substituted alkyl or optionally substituted aryl; A is a group of Formula (2) :
B-N = N- Formula (2) in which B is an aryl or heterocyclic group each of which may be optionally substituted; or A is a group of Formula (3) :
Figure imgf000003_0002
Formula (3) in which R6 is -H or alkyl, alkenyl or aralkyl each of which may be optionally substituted, -SO,alkyl, SO, aryl or -COR in which R is -H or alkyl, aryl, cycloalkyl or aralkyl each of which may be optionally substituted;
R7 is an electron withdrawing group; provided that when A is a group of Formula (3) , Z is a direct link, R2 and R2 are both methyl and R4 is H that R1 is selected from methyl, ethyl, n- and isαpropyl, tertiary butyl, n-pentyl, n-hexyl, n- heptyl, n-octyl or provided that when A is a group of Formula (3) and Z is a direct link that R4 is alkyl, -NHCOalkyl, -NHCOaryl, -NHSO,alkyl, or -NHSO,aryl; or provided that when R7 is -CN and Z is -C(CH3)- that R4 is not -H; or
A is an optionally substituted group of Formula (4) :
Figure imgf000004_0001
Formula (4) in which and L are optional substituents or a form a 5- or 6-membered carbocyclic or heterocyclic ring with the carbon atoms to which they are attached; or
A is a group of Formula (5) :
Figure imgf000004_0002
in which Formula (5)
R10 is -CH or N; and Ring D may be optionally substituted by from 1 to 5 substituents; or
A is a group of Formula (6) :
Figure imgf000004_0003
Formula (6) in which R11 and Rι: each independently is an electron withdrawing group; and R13 is -H or -CN; or
A is a group of Formula (7)
Figure imgf000005_0001
Formula (7) in which R14 and R15 is aryl; or
A is a group of Formula (8)
Figure imgf000005_0002
Formula (8)
in which R16 is N or C-R is as hereinbefore defined; or A is a group of Formula (9) :
Figure imgf000005_0003
Formula (9)
in which Ring F is optionally substituted by from 1 to 5 groups and E is carbocyclic or heterocyclic; or A is a group of Formula (10) :
Figure imgf000005_0004
Formula (10) in which R17 is optionally substituted aryl or a group of Formula (16B) :
Figure imgf000006_0001
Formula (16B)
The alkyl group represented by R, R1, R2, R3, R4, R5, R6 is preferably C1-20 -alkyl, more preferably
Figure imgf000006_0002
and especially C._B- alkyl. The cycloalkyl group represented by R and R1 is preferably C4_β- cycloalkyl, more preferably cyclohexyl.
The aryl group represented by R, R1, R5, R14, R1S and R17 is preferably phenyl or naphthyl.
The alkenyl group represented by R1 and R6 is preferably C-,.10- alkenyl, more preferably C-,_6-alkenyl and especially C^-alkenyl such as allyl or vinyl.
The aralkyl group represented by R, R1 and RG is preferably aryl CL_ 6-alkyl, more preferably phenyl C-.-5-alkyl, especially phenyl C*,.3-alkyl such as benzyl, phenylethyl, chlorobenzyl or nitrobenzyl. Where R4 is -NHCOalkyl it is preferably -NHCOC1.6-alkyl, more preferably -NHCOCi.,.-alkyl and especially -NHCOCH3 or -NHCO H*.
Where R4 is alkoxy it is preferably C^;,-alkoxy and more preferably Cj-B-alkoxy.
Where R6 is -S02alkyl it is preferably -SO-A^-alkyl. Where R6 is -S02aryl it is preferably -S02phenyl.
Where R7, R11, R12 are electron withdrawing groups they are preferably -C , -S02F, -COOR8, -C0NR8R9, -S02R8 in which R8 and R9 each independently is -H or any of the groups defined above for R1.
Where B is an aryl group it is preferably phenyl or naphthyl. Where B is a heterocyclic group it is preferably thienyl, thiazolyl, isothiazolyl, pyridyl, pyrazolyl, thiadiazolyl, imidazolyl, oxazolyl, benzoisothiazolyl and more preferably thienyl, isothiazolyl, and pyrazolyl and especially thienyl and isothiazolyl. B is preferably phenyl, naphthyl, thienyl, isothiazolyl or pyrazolyl especially phenyl or isothiazolyl.
Where any of the groups represented by R, R1 to R9, R17, B, Ring D, Ring F or the group of Formula (4) are optionally substituted the optional substituents may be selected from -NO,, -CN, -OH, -Cl, -F, -Br, -SCN, phenyl, alkyl, alkoxy, alkoxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonyloxy, phenoxylalkyl, alkylcarbonyloxy, alkoxyalkoxycarbonyloxy, alkylcarbonyloxy, phenoxyalkoxycarbonyl, -NReR9, -COR8, -C02R8 in which R8 and R9 are as hereinbefore defined, -NHCOalkyl and -NHS02alkyl in each of the above substituents each alkyl is preferably C1-4-alkyl and each alkoxy is preferably C^-alkoxy. Preferred substituents are -N02, -CN, -CO,R8, alkyl, -SCN, -COR8, -Cl and -Br. K and L may be any of the optional substituents listed above.
The alkyl groups represented by R and R1 to R6, R8 and R9 and alkyl and alkoxy substituents listed above may be straight or branched chain alkyl or alkoxy groups.
Where E is carbocyclic it is preferably of Formula (17A) or (17B) :
Figure imgf000007_0001
Formula (17A)
Formula (17B)
and may carry any of the optional substituents defined above. Where E is heterocyclic it is preferably of Formula (18) :
Figure imgf000007_0002
Formula (18) or of Formula (19) :
Figure imgf000007_0003
Formula (19) in which R7 is as hereinbefore defined and R18 is -H, C1_4-alkyl, -F, -Cl or -Br.
A is preferably a group of Formula (2) , Formula (3) , Formula (4) , Formula (9) or Formula (10) , more preferably a group of Formula (2) or Formula (4) . In dyes of Formula (1) R1 is preferably C^e-alkyl, more preferably an α-branched C3.e-alkyl or a straight chain C1-B-alkyl and especially 1-methylhexyl, n-heptyl, n-butyl, iεobutyl R2 and R3, are preferably Ci-e-alk l, more preferably C^-alkyl and especially methyl, R4 is preferably -H, C1-β-alkyl, -NHCOCi.a-alkyl, -OH or C1-B-alkoxy more preferably -H, C1-4-alkyl or -NHCOCj.-4-alkyl and especially -H, methyl or -NHCOmethyl or -NHCOethyl.
A particularly preferred group of dyes Formula (1) are those in which R2 and R3 are both methyl. A preferred sub-group of dyes of Formula (1) are those of Formula
(11) :
Figure imgf000008_0001
Formula (11)
in which R1, R2, R3 and R4 are as hereinbefore defined; and Ring C carries from 1 to 5 optional substituents selected from those listed above.
A further preferred sub group of dyes of Formula (1) are those of Formula (12) :
Figure imgf000008_0002
Formula (12) in which R1, R2, R3 and R4 are as hereinbefore defined; X is -CN, or halogen; and
Y is Ci.s-alkyl optionally substituted by C1_4-alkoxy or pyridyl.
A further preferred sub group of dyes of Formula (1) are those of Formula (13) :
Figure imgf000009_0001
Formula (13)
in which R1, R2, R3 and R4 are as hereinbefore defined; Rε is -H, C1-8-alkyl or -CH-phenyl; and R7 is -CN or -COOC1-B-alkyl. Preferred dyes of Formula (13) are those in which R1 is n-pentyl, n-hexyl, n-heptyl or isobutyl, R2 and R3 are both methyl, R4 is -H, -CH3 or -NHCOCH3, R~ is -H and R7 is -CN. Especially preferred dyes of Formula (13) are those in which R1 is n-heptyl or isobutyl, R2 and R3 are both methyl, R4 is -H, -CH3 or -NHCOCH*, R6 is -H and R7 is -CN. A further preferred sub group of dyes of Formula (1) are those of
Formula (14) .
Figure imgf000009_0002
in which R1, R2, R3 and R4 are as hereinbefore defined, R6 is -H, Ci-e-alkyl or -OLphenyl; and R7 is -CN or -COOC1-8-alkyl.
A further preferred subgroup of dyes of Formula (1) are those of Formula (15) .
Figure imgf000010_0001
Formula (15) in which R1, R2, R3 and R4 are as hereinbefore defined; and X1 is -H, C1-8- alkyl or -NHCOC1-a-alkyl.
The dyes of Formula (1) may be prepared by reacting a compound of Formula (16) :
Figure imgf000010_0002
with a compound of Formula A-X. Where A is a group of Formula (2) X is a diazonium salt prepared by diazotisation, using conventional reaction conditions, of the corresponding amine, A-NH-,.
Where A is a group of Formula (3) X is halogen preferably -Cl or -Br and the reaction may be performed in a liquid medium such as N, N- dimethylformamide or N, N-dimethylacetamide at a temperature from -20°C to 50°C. The product may be isolated by any convenient means such as pouring the reaction product into water and recovering the precipitated product by filtration.
Dyes of Formula (1) in which A is a group of Formula (4) may be prepared by oxidative coupling of a phenol with a coπpound of Formula (1) in which A is -NH_, using an oxidising agent such as an alkali metal persulphate, alternatively by nitrosation of a compound of Formula (1) in which A is H and reaction with a phenol in the presence of acetic anhydride.
Dyes of Formula (1) in which A is a group of Formula (5) may be prepared by reaction of a coπpound of Formula (1) in which A is -CHO or -NO with a coπpound of Formula (5B) :
Figure imgf000011_0001
in the presence of catalytic amounts of an organic base such as piperdine.
The coπpound of Formula (5B) may be obtained by reaction of malononitrile with benzoylacetonitrile.
Dyes of Formula (1) in which A is a group of Formula (6) and R13 is H may be prepared by condensation of a coπpound of Formula (1) in which A is -CHO with an active methylene coπpound such as alonitrile or an alkylcyanoacetate such as ethylcyanoacetate.
Dyes of Formula (1) in which A is a group of Formula (6) and R13 is -CN may be prepared by reaction of a compound of Formula (1) in which A is -H with tetracyanoethylene in an organic liquid such as dimethylformanide.
Dyes of Formula (1) in which A is a group of Formula (7) may be prepared by reaction of a coπpound of Formula (1) where A is -CHO with a diaryldiketσpyrrole.
Dyes of Formula (1) in which A is a group of Formula (8) may be prepared by reacting a compound of Formula (1) where A is -NIL, or -NO with a compound of Formula (8B) :
Figure imgf000011_0002
Formula (8B)
where X is a displaceable atom or group such as -H or -Cl.
Dyes of Formula (1) in which A is a group of Formula (9) may be prepared by coupling a coπpound of Formula (1) in which A is -H with a diazotised coπpound of Formula (9B) :
Figure imgf000011_0003
Formula (9B) Dyes of Formula (1) in which A is a group of Formula (10) may be prepared by reacting a coπpound of Formula (10B) :
Figure imgf000012_0001
Formula (10B) with a coπpound of Formula (16) in an acid medium.
The conpound of Formula (16) may be prepared by reacting an indoline or piperazine of Formula (16) in which R1 is -H with a coπpound of Formula R1-Y in which Y is a halogen such as -Cl, -Br or I or a tosylate or mesylate in the presence of an alkali or alkaline earth metal carbonate. Alternatively the coπpound of Formula (16) in which Z is a direct link may be prepared by reaction of an aniline firstly with a coπpound R'-Y to replace one of the -H atoms attached to the N atom followed by reaction with a haloalkene such as 3-chloro-2-methylpropene in the presence of a base such as NaH or ,C03 in a liquid medium such as dimethylformamide or tetrahydrofuran to form an N-alkyleneaminobenzene followed by ring closure by heating at about 140°C in a liquid medium such as xylene in the presence of a Lewis acid such as ZnCl, or a protic acid such as H3P04 or H,S04.
The compounds of Formula (16) in which
R1 is alkyl, cycloalkyl, aryl, alkenyl or aralkyl each of which may be optionally substituted;
R2 and R3 each independently is optionally substituted alkyl;
R4 is -H or alkyl, -NHCOalkyl each of which may be optionally substituted; and
Z is a direct link, oxygen or -N-R5 in which R5 is -H, optionally substituted alkyl or optionally substituted aryl except for the following compounds in which:
R5
Figure imgf000012_0002
Me Me CH,CH=CHCOOMe H Direct Link
Me Me Me H N-R5 Me
form a further feature of the present invention. The use of a group of Formula (16B) in a dye molecule forms a further feature of the present invention. Compared with open chain analogues introduction of such a group generally improves the properties of dyes particularly improving light fastness properties and induces into a dye molecule a bathochromic shift in the λ max. value of the dye for exaπple a typical shift of approximately 20-30nm is obtained in dyes in which A is a group of Formula (3) and has the advantage of allowing shade changes to be conveniently obtained.
The dyes of the present invention may be used for .the coloration of textile materials preferably synthetic textile materials and more preferably polyester such as polyethylene terephthalate, polyamide such as polyhexamethylene adipamide, polyurethane elastomers, cellulose acetate and triacetate and for fibre blends thereof such as polyester- cotton, polyester-wool and polyester-viscose. These uses form further features of the present invention. The textile materials may be in the form of filaments, loose fibres, yarn or may be in the form of woven or knitted fabrics. The present dyes, optionally in mixtures with themselves or with other disperse dyes such as those from the monoazo, disazo, trisazo, anthraquinone, benzodifuranone, methine, quinophthalone, nitro, flavone, dioxopyrrole, squariluim, coumarin, naphthalamide, naphtholactam, triphendioxazine, indoaniline, indophenol, and hydrazone dye classes, may be applied to the textile materials by methods eπployed in applying disperse dyes to such materials for exaπple by exhaust dye, continuous dyeing, printing and discharge printing using the conditions and additives conventionally used in carrying out such processes. The mixtures of dyes referred to above form a further feature of the present invention particularly preferred dye mixtures comprise from 5% to 95% of one or more dyes of Formula (1) and from 95% to 5% of one or more monoazo, disazo, anthraquinone or indoaniline dyes. The dyes of the present invention generally have good to excellent light and wash fastness and show improved build up on textile materials. Mixtures of two or more different dyes of Formula (1) or mixtures of dye types described above generally show improvements in dyeing properties. In addition to their use for the coloration of textile materials the present dyes may also be used in a variety of coloration processes for example in coatings on thermal transfer printing sheets which are used in a dye diffusion thermal transfer printing process, in inks for ink-jet printing, in coloured toners for use in electroreprography. The invention is illustrated by the following exatrples: Example 1 Preparation of:
Figure imgf000014_0001
i) A mixture of N- (2-methylprop-2-en-3-yl) -N-isobutylaniline (6.1g) and zinc chloride (3.9g) in m-xylene (50cm3) was heated under reflux for 24 hours before dissolving in dichloromethane and filtering. The dichloromethane solution was washed with water, separated and dried over anhydrous magnesium sulphate. The magnesium sulphate was removed by filtration and the dichloromethane was separated to leave a crude oil which was purified by elution from silica with a 9:1 mixture of hexane:dichloromethane. The solvent was evaporated to leave 2,2- dimethyl N-isobutylindoline (4.3g, 71.4%) as a colourless oil. ii) 2,2-dimethyl N-isobutylindoline (1.2g), disodium salt of 4-cyano- 5-dicyanomethylidene-3-hydroxy-2-oxo-2,5-dihydropyrrole (1.32g), acetic anhydride (0.5cm3) and dimethylformamide (25cm3) were mixed and cooled to -1°C. Phosphorus oxychloride (5.0g) was added drσpwise stirring the reaction mixture at 0°C for 1 hour. The reaction mixture was allowed to warm to ambient temperature before pouring into ice and isolating the precipitate by filtration.
The solid obtained was dried under vacuum at 60°C to yield the title coπpound (1.5g, 70%) m.p.t. 278-280°C.
Example 2 Preparation of:
Figure imgf000014_0002
2,2-Dimethyl N-isobutylindoline (l.Olg) and tetracyanoethylene (0.64g) in dimethylformamide (6cm3) was heated at 60°C for 10 minutes before cooling in ice and adding water. The aqueous mixture was extracted with dichloromethane, the dichloromethane was dried over magnesium sulphate, filtered and evaporated to give the title coπpound (1.07g, 70.4%), m.p.t. 156-157°C, λmax = 546nm, m/Z = 304.
Figure imgf000015_0003
Figure imgf000015_0001
i) A mixture of 2,2-dimethyl N-isobutylindoline (2.0g) and concentrated hydrochloric acid (4.5cm3) was cooled to 8°C and sodium nitrite (0.8g) in water (2cm3) was added drqpwise. The reaction mixture was allowed to warm to ambient temperature, made alkaline with sodium hydroxide solution an extracted with ethyl acetate. The ethyl acetate was dried over magnesium sulphate, filtered and evaporated to give 5-nitroso-2,2-dimethyl N-isobutyl indoline. ii) 5-nitroso-2,2-dimethyl N-isobutyl indoline from i) , 2-amino-l,1,3- tricyanσprop-2-ene (0.66g) methylated spirits (50cm3) and sodium hydroxide solution (10%, 2 drops) were heated under reflux for 1 hour before cooling and evaporating the solvent. The residue was eluted from silica using 50: (dichloromethane) methanol as eluent. Evaporation of the solvent gave the title coπpound m.p. 173-175°C, λmax = 560nm, m/Z = 346.
Example 4 Preparation of:
Figure imgf000015_0002
5-Nitroso-2,2-dimethyl N-isobutyl indoline (1.16g), 2- acetamidophenol (0.76g), acetic anhydride (1cm3) and methylated spirits (50cm3) was stirred at room temperature for three days before filtering. The filtrated were evaporated to leave a residue which was eluted from silica using 50:50 ethylacetate/hexane as eluent. Evaporation of the solvent gave the title coπpound λmax = 649nm, m/Z = 365.
Example 5 Preparation of:
Figure imgf000016_0001
i) N- (2-methylprop-2-en-3-yl)N-n-heptyl aniline (0.38 mole), zinc chloride (0.4 mole) and m-xylene (200cm3) were refluxed for 17 hours before cooling and dissolving in dichloromethane. The dichloromethane was filtered and washed with water, separated, dried over magnesium sulphate, filtered and evaporated to leave an oil. The oil was eluted from silica using 50:50 dichloromethane/hexane as eluent evaporated of the solvent gave 2,2-dimethyl-N-n-heptylindoline (122g, 95.8%) . ii) To 2,2-dimethyl-N-n-heptylindoline (12.5g) in dimethylformamide (100cm3) phosphorus oxychloride (15.3g) was added at 5°C before heating the mixture at 80°C for 2-5 hours. The reaction mixture was cooled, poured onto ice, neutralised with solid sodium carbonate and extracted into toluene. The toluene was washed with water, separated, dried over magnesium sulphate, filtered and evaporated to leave an oil. The oil was eluted from silica using dichloromethane as eluent, evaporation of the solvent gave 2,2-dimethyl-5-formyl-N-n-heptylindoline (4.9g, 36.1%). ii) 2,2-dimethyl-5-formyl-N-n-heptylindoline (l.lg), malononitrile
(0.27g), methylated spirits (20cm3) and piperdine (2 drops) was stirred at room temperature for 2 days. The solvent was evaporated and the residue eluted from silica using dichloromethane as eluent. Evaporation of the dichloromethane gave the title coπpound (0.9g, 69.6%), λmax = 454nm, m/Z = 321.
Example 6 Preparation of:
Figure imgf000017_0001
2,2-dimethyl-5-formyl-N-n-heptylindoline (l.lg), ethylcyanoacetate (0.46g), methylated spirits (10cm3) and piperdine (2 drops) were stirred at room teπperature for 1 day before evaporating the solvent to leave an oil. The oil was eluted from silica using dichloromethane as eluent. Evaporation of the solvent gave the title coπpound λmax = 444nm, m/Z = 368.
Example 7 Preparation of:
Figure imgf000017_0002
2,2-dimethyl-5-for yl-N-n-heptylindoline (l.lg), 2-phenyl-l,1,3- tricyanαprop-2-ene (0.78g), methylated spirits (20cm3) and piperdine (2 drops) were stirred at room temperature for 5 hours before evaporating the solvent to leave a residue which was eluted from silica using 80:20 hexane/ethylacetate as eluent. Evaporation of the solvent gave the title coπpound (1.5g, 83.1%) λmax = 548nm, m/Z = 448.
Example 8
Preparation of:
Figure imgf000017_0003
Acetic acid (60cm3) , propionic acid (11cm3) and sulphuric acid (3cm3) were mixed and cooled to less than 5°C before adding nitrosylsulphuric acid (9.3cm3) at less than 5°C. After stirring for 15 minutes 2-bromo-4,6-dinitroaniline (3.51g) was added and the mixture was stirred for 1.5 hours at less than 5°C.
2,2-dimethyl N-n-butylindoline (2.0g) was dissolved in methanol (100cm3) and cooled to less than 5°C and the diazo solution added slowly at 5°C. After 1 hour sodium acetate was added to adjust the pH to 4. The mixture was filtered and the separated solid washed with water. The solid was dissolved in acetone, dried over magnesium sulphate, filtered and evaporated to give the title coπpound (1.26g, 26.5%) λmax = 582nm.
Exaπples 9 to 20 were prepared using the method of Exaπple 8, these exaπples are summarised in Table 1.
Table 1
Figure imgf000019_0001
Table 1 Cont'd
Figure imgf000020_0001
Table 1 Cont'd
Figure imgf000021_0001
Table 1 Cont'd
Figure imgf000022_0001
Example 21 Preparation of:
Figure imgf000023_0001
A mixture of 4- (4-methylphenylazo) aniline (1.6g), acetic acid (43cm3) , propionic acid (7cm3) was cooled to less than 10°C and nitrosyl sulphuric acid (3.0cm3) was added, the mixture was stirred at 5°C for 45 minutes before adding to a mixture of 2,2-dimethyl N-n-heptylindoline (2.0g) in acetic acid (50cm3) . The reaction mixture was poured into ice/water and sodium acetate was added. The reaction mixture was extracted into ethyl acetate evaporation of which gave the title compound (1.08g). λmax - 510nm, m/Z = 467.
Example 22 Preparation of:
Figure imgf000023_0002
A mixture of 3-hydroxy-7- (4-n-prαpoxyphenyl)-2,6-dioxo-2,6- dihydrobenzo- [l:2-b,4:5-b'] -difuran (0.7g), acetic acid (23.8cm3), sulphuric acid (1.2cm3) and 2,2-dimethyl-N-n-heptylindoline (0.6g) was heated at 1 0°C for 12 hours before pouring into a mixture of ice and water to precipitate a solid which was isolated by filtration. The solid was eluted from silica using dichloromethane as eluent evaporation gave the title coπpound (0.48g) λmax = 702nm, m/Z = 565.
Example 23 Preparation of:
Figure imgf000024_0001
A mixture of 7-phenyl-7-H-benzodifuran-2,3,6-trione (1.4g), acetic acid (47.5cm3), sulphuric acid (2.5cm3) and 2,2-dimethyl-N-n-heptylindoline (1.25g) was stirred at 140°C for 10 hours before pouring into ice/water. The precipitated solid was isolated by filtration and purified as in
Exaπple 21 to give the title coπpound (0.76g) λmax = 712nm, m/Z = 507.

Claims

A disperse dye of Formula (1)
Figure imgf000025_0001
Formula (1) in which R1 is alkyl, cycloalkyl, aryl, alkenyl or aralkyl each of which may be optionally substituted;
R2 and R3 each independently is optionally substituted alkyl;
R4 is -H, -OH or alkyl, alkoxy, -NHCOalkyl, -NHCOaryl, - NHS02alkyl, -NHS02aryl each of which may be optionally substituted; Z is a direct link, oxygen or -N-R5 in which R5 is -H, optionally substituted alkyl or optionally substituted aryl; A is a group of Formula (2) :
B-N = N- Formula (2) in which B is an aryl or heterocyclic group each of which may be optionally substituted; or
A is a group of Formula (3) :
Figure imgf000025_0002
Formula (3) in which
R6 is -H or alkyl, alkenyl or aralkyl each of which may be optionally substituted, -S02alkyl, S02 aryl or -COR in which R is -H or alkyl, aryl, cycloalkyl or aralkyl each of which may be optionally substituted; R7 is an electron withdrawing group; provided that when A is a group of Formula (3) , Z is a direct link, R2 and R3 are both methyl and R4 is H that R1 is selected from methyl, ethyl, n- and isoprcpyl, tertiary butyl, n-pentyl, n-hexyl, n- heptyl, n-octyl or provided that when A is a group of Formula (3) and Z is a direct link that R4 is alkyl, -NHCOalkyl, -NHCOaryl, -NHSO-alkyl, or -NHSO,aryl or provided that when R7 is -CN and Z is -C(CH3)- that R4 is ot -H; or
A is an optionally substituted group of Formula (4) :
Figure imgf000026_0001
Formula (4) in which K and L are optional substituents or a form a 5- or 6-membered carbocyclic or heterocyclic ring with the carbon atoms to which they are attached; or A is a group of Formula (5) :
Figure imgf000026_0002
in which R10 is -CH or N; and
Ring D may be optionally substituted by from 1 to 5 substituents; or
A is a group of Formula (6) :
Figure imgf000026_0003
Formula (6) in which R11 and R12 each independently is an electron withdrawing group; and
R13 is -H or -CN; or A is a group of Formula (7) :
Figure imgf000027_0001
in which R14 and R15 each independently is aryl; or A is a group of Formula (8) :
Figure imgf000027_0002
Formula (8)
in which R1S is N or C-R is as hereinbefore defined; or A is a group of Formula (9) :
Figure imgf000027_0003
Formula (9)
in which Ring F is optionally substituted by from 1 to 5 groups and E is carbocyclic or heterocyclic; or A is a group of Formula (10) :
Figure imgf000027_0004
Formula (10) in which R17 is optionally substituted aryl or a group of Formula (16B) :
Figure imgf000028_0001
Formula (16)
2. A dye of Formula (1) in which A is a group of Formula (2) and B is selected from phenyl, naphthyl, thienyl, thiazolyl, isothiazolyl, pyridyl, pyrazolyl, thiadiazolyl, imidazolyl, oxazolyl, benzoisothiazolyl.
3. A dye of Formula (1) in which A is a group of Formula (3) in which R7 is -CN, -S02F, -C00Rθ, -CONRBR9 or -S02R8 in which R8 and R9 each independently is -H or any of the groups defined for R1 provided that when A is a group of Formula (3) , Z is a direct link, R2 and R3 are both methyl and R4 is H that R1 is selected from methyl, ethyl, n- and isσprαpyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or provided that when A is a group of Formula (3) and Z is a direct link that R4 is alkyl, -NHCOalkyl, -NHCOaryl, -NHSO,alkyl, or -NHS02aryl; or provided that when R7 is -CN and Z is -C(CH3)- that R4 is not -H.
4. A dye of Formula (1) in which A is a group of Formula (4) in which K and L each independently is selected from -N02, -CN, -OH, -Cl, -F, - Br, phenyl, alkyl, alkoxy, alkoxyalkoxy, alkylcarbαnyl, alkoxycarbonyl, alkylalkoxycarbonyl, alkoxyalkoxycarbonyl, alkoxycarbonyloxy, phenoxylalkyl, alkylcarbonyloxy, alkoxyalkoxycarbonyloxy, alkylcarbonyloxy, phenoxyalkoxycarbonyl, -NRβR9, -COR", -C02R8 in which R8 and R9 are as hereinbefore defined, -NHCOalkyl and -NHSO,alkyl in each of the above substituents each alkyl is preferably C^-alkyl and each alkoxy is preferably C-^-alkoxy.
5. A dye of Formula (1) in which A is a group of Formula (9) in which E is of Formula (17A) or (17B) :
Figure imgf000028_0002
Formula (17A)
Figure imgf000028_0003
Formula (17B) or of Formula (18)
Figure imgf000029_0001
Formula (18)
or of Formula (19)
Figure imgf000029_0002
Formula (19)
in which R18 is -H, C1-4- alkyl , -F, -Cl or -Br.
6. A dye of Formula (1) in which A is a group of Formula (10)
Figure imgf000029_0003
Formula (10) in which R17 is optionally substituted phenyl or naphthyl or a group of Formula (16B) :
Figure imgf000029_0004
Formula (16B)
7. A coπpound of Formula (16)
Figure imgf000030_0001
Formula (16) in which
R1 is alkyl, cycloalkyl, aryl, alkenyl or aralkyl each of which may be optionally substituted;
R2 and R3 each independently is optionally substituted alkyl;
R4 is -H or alkyl, -NHCOalkyl each of which may be optionally substituted; and
Z is a direct link, oxygen or -N-R5 in which R5 is -H, optionally substituted alkyl or optionally substituted aryl except for the following compounds in which:
Figure imgf000030_0002
Me
PCT/GB1995/000675 1994-04-19 1995-03-27 Disperse dyes derived from hindered indoline couplers WO1995028447A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104710809A (en) * 2013-12-16 2015-06-17 上海安诺其集团股份有限公司 Bright yellow disperse dye
KR20200008466A (en) * 2018-07-16 2020-01-28 한국화학연구원 Azo based disperse dyes for supercritical fluid dyeing and method for preparing the same
KR20210061620A (en) * 2019-11-20 2021-05-28 한국화학연구원 Azo based reactive-disperse dyes for supercritical fluid dyeing and supercritical fluid dyeing using the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59152956A (en) * 1983-02-17 1984-08-31 Sumitomo Chem Co Ltd Tricyanostyril and dyeing or coloring therewith
JPS59193961A (en) * 1983-04-19 1984-11-02 Gosei Senriyou Gijutsu Kenkyu Kumiai Disazo dye for polyester fiber
GB2191498A (en) * 1986-05-21 1987-12-16 Nippon Kayaku Kk Pyrroline derivatives, their preparation and their use as colouring agents
EP0363034A2 (en) * 1988-10-03 1990-04-11 Zeneca Limited Polycyclic dyes
EP0462928A2 (en) * 1990-06-19 1991-12-27 Ciba-Geigy Ag Indolinimin dyes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59152956A (en) * 1983-02-17 1984-08-31 Sumitomo Chem Co Ltd Tricyanostyril and dyeing or coloring therewith
JPS59193961A (en) * 1983-04-19 1984-11-02 Gosei Senriyou Gijutsu Kenkyu Kumiai Disazo dye for polyester fiber
GB2191498A (en) * 1986-05-21 1987-12-16 Nippon Kayaku Kk Pyrroline derivatives, their preparation and their use as colouring agents
EP0363034A2 (en) * 1988-10-03 1990-04-11 Zeneca Limited Polycyclic dyes
EP0462928A2 (en) * 1990-06-19 1991-12-27 Ciba-Geigy Ag Indolinimin dyes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 102, no. 16, 22 April 1985, Columbus, Ohio, US; abstract no. 133542z, "blue disazo disperse dyes for polyester fibers" page 78; *
CHEMICAL ABSTRACTS, vol. 102, no. 4, 28 January 1985, Columbus, Ohio, US; abstract no. 26385d, "tricyanostyryl dyes" page 96; *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104710809A (en) * 2013-12-16 2015-06-17 上海安诺其集团股份有限公司 Bright yellow disperse dye
CN104710809B (en) * 2013-12-16 2017-07-18 上海安诺其集团股份有限公司 A kind of bright yellow disperse dyes
KR20200008466A (en) * 2018-07-16 2020-01-28 한국화학연구원 Azo based disperse dyes for supercritical fluid dyeing and method for preparing the same
KR102124602B1 (en) * 2018-07-16 2020-06-18 한국화학연구원 Azo based disperse dyes for supercritical fluid dyeing and method for preparing the same
KR20210061620A (en) * 2019-11-20 2021-05-28 한국화학연구원 Azo based reactive-disperse dyes for supercritical fluid dyeing and supercritical fluid dyeing using the same
KR102260181B1 (en) 2019-11-20 2021-06-03 한국화학연구원 Azo based reactive-disperse dyes for supercritical fluid dyeing and supercritical fluid dyeing using the same

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