CA2519157A1 - New heterocyclic compounds, a process for their preparation and their use as dyes and pigments - Google Patents
New heterocyclic compounds, a process for their preparation and their use as dyes and pigments Download PDFInfo
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- CA2519157A1 CA2519157A1 CA002519157A CA2519157A CA2519157A1 CA 2519157 A1 CA2519157 A1 CA 2519157A1 CA 002519157 A CA002519157 A CA 002519157A CA 2519157 A CA2519157 A CA 2519157A CA 2519157 A1 CA2519157 A1 CA 2519157A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/36—One oxygen atom
- C07D263/40—One oxygen atom attached in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
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- Plural Heterocyclic Compounds (AREA)
Abstract
Compounds of formula (I) wherein R1 is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, R'1 is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic arnide, alkylthio, arylthio, alkoxy or aryloxy, X is -O-, -S-, -NH- or -N(alkyl)-, X' is -0-, -S-, -NH- or -N(alkyl)-, Y is hydrogen or carboxylic ester, Y' is hydrogen or carboxylic ester, Z is =C- or =N-, Z' is =C- or =N-, x is 0 or 1, when Z is =N-, then x is 0, y is 0 or 1, when Z' is =N-, then y is 0, A is a conjugated linking bridge of the formulae (II), (III), (IV), (V), or (VI), wherein n is 0, 1, 2 or 3, m is 0, 1, 2 or 3, B is a phenyl ring, T is =C(R3)- or =N-, wherein R3 is hydrogen, C1-C12alkyl or CN, W is a heterocyclic, or linear or polycondensed aromatic group which is unsubstituted or substituted by alkyl, halogen, hydroxy, alkoxy, alkylthio or amino, G is -CH= or -N=, and R2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino, their preparation and their use in the production of coloured plastics or polymeric color particles.
Description
NEW HETEROCYCLIC COMPOUNDS, A PROCESS FOR THEIR PREPARATION AND
THEIR USE AS DYES AND PIGMENTS
The present invention relates to new compounds, to their preparation and to their use in the production of coloured plastics or polymeric colour particles.
The subject of the present invention are compounds of formula (1) O
X' R~
Z A Z' ~ (1), I R'~
X ~Y~)v ~
O
wherein R~ is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, Garb~xylic ester, sulfo, sulfo-nic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, R', is hydrogen, Ilydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfo-nic ester, carboxylic amide, sulfonic amide, alkyltllio, arylthio, alkoxy or aryloxy, X is -O-, -S-, -NH- or-N(alkyl)-, X' is -O-, -S-, -NH- or-N(alkyl)-, Y is hydrogen or carboxylic .ester, Y' is hydrogen or Garb~xylic ester, Z is =C- or =N-, Z' is =C- or =N-, x is 0 or 1, when Z is =N-, then x is 0, y is 0 or 1, when Z' is =N-, then y is 0, A is a conjugated linking bridge of the formula Rz T
j , ~T.~ /~ / , ~ g /TAW / or L" JrriT I / / ' vT/
JnT/
Rz Rz iT ~~/ G G ~ / Ti, wherein n is 0, 1, 2 or 3, m is 0, 1, 2 or 3, B is a phenyl ring, T is =C(R3)- or =N-, wherein R3 is hydrogen, C~-C~2alkyl or CN, W is a heterocyclic, or linear or polycondensed aromatic group which is unsubstituted or sub-stituted by alkyl, halogen, hydroxy, alkoxy, alkylthio or amino, G is -CH= or-N=, and Rz is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino.
According to the invention an alkyl is for example a straight-chain or branched C~_$alkyl as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl or octyl, prefe-rence being given to a C,_4alkyl.
According to the invention an alkylthio is for example methylthio, ethylthio, propylthio, butyl-tllio, lleptylthio or hexylthio.
According to the invention an alkoxy is for example a straight-chain or branched C,_$alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.
butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1,1,3,3-tetramethylbutoxy or 2-ethylhexyloxy.
According to the invention an aryloxy is to be understood as being for example a C6_~øaryl-oxy, preferably a C6_~~arylOxy radical, for example phenoxy or 4-methylphenoxy.
According to the invention an arylthio is for example phenylthio or napthylthio.
G is preferred -CH=.
W as aromatic group includes, for example, phenylene, naphthalene, acenaphthylene, anthracene, phenanthrene, naphthacene, chrysene, pyrene or perylene. W is preferably phe-nylene, naphthalene, anthracene, phenanthrene, perylene or pyrene, and most preferably phenylene or naphthalene.
W as heterocyclic group is, for instance, pyridine, pyrazine, pyrimidine, pyridazine, indole iso-indole, quinoline, isoquinoline, carbazole, phenothiazine, benzimidazolone, benzothiazole, pyrrolo, imidazole, pyrrolidine, piperidine, piperazine, morpholine or pyrazole.
According to the invention an ester is for example methyl-, ethyl-, propyl- or butylester.
If A is a single double bond / , preferred compounds of formula (1 ) are a) compounds of phenyl-butyrolactams of formula / ~ EtOZC N -H / H N -H
i /
R1 \ C C/ / , R1 \ ~ / C~ / and H- N CO Et \ R1 I R1 z H- N H \
~ O
O
R / ~ EtOZC N -nC4H9 ~ \ C / Ci /
H9CQn- N COzEt \
O
b) compounds of phenyl-butyrolactones of formula O
/ H O
\ ~ / O~ / , O H \
O
c) compounds of phenyl oxazolones of formula O
O
\ N / Ni O \ H1 O
and d) compounds of phenyl imidazolones of formula O
/ ~ N -H
R~
\ N / Ni /
R~
H- N \
O
wherein R, has the meaning given under the formula (1 ) and Et is -CH2CH3.
If A is a conjugated linking bridge, preferred compounds of formula (1 ) are e) compounds of phenyl-carboethoxy-butyrolactams of formula / CO~Et RZ
R ~ ~ O H
\ N, and N
H, ~ n C \
R~ C~~Et ~ / R1 n=0, 1 or2 / COZEt R~
R ~ I O nBut \ N.
N /
nBllt~~ O n ~ \
_. ~ _ _. ~ R~
f) compounds of phenyl-butyrolactones of formula R / ~ H R~
~c / ~ \ o o / r Q n C \
I I R~
RZ H /
n=0, 1 or2 n=0, 1 or2 ~g) compounds of phenyl-butyrolactams of formula \ C
N-H O ~ J n" ~j I I ~ R1 h) compounds of phenyl-oxazolones of formula / R
R z O
1 \ iN / \ O
O L I / /
O ~ 'N \
Rz I /
n=0, 1 or2 and i) compounds of phenyl-imidazolones ~f formula R
R1 \ I N z O H
/ \ N.
N I / /
H, O ~ , N I \
n=0, 1 or2 wherein R1 and R2 have the meaning given under the formula (1 ), Et is -CHzCH3 and nEut is n-butanole.
Further preferred are compounds of formula (1 ), wherein R1 is hydrogen, chloro, bromo, methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro is, R~1 is hydrogen, chloro, bromo, methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro, RZ is hydrogen or methoxy, X is -NH-, -N(n-C4H9)-, or -O-, X is -NH-, -N(n-C4H9)-, or -O-, Y is hydrogen or COOCzHS, Y is hydro-gen or COOC2H5, Z is =C- or =N-, Z~ is =C- or =N-, A is = or -T ~ g ~ T = , n T is =C(R3)-, R3 is hydrogen and n is 0, 1 or 2.
n=0, 1 or2 The most preferred compounds of formula (1) are the compounds of the formulae O
I o C o C~ , (100), o H wl I o C C ~~~ o (101 ), ' ' \ / H H ~
O
I o C C C~~ o (102), ~H H ~
O
O
O
I o N C C~~ o (103), / H
O- ~ w O
O
O
I o C C Ci\C' o (104), ' \ / \ / H H
O
O
O
O
I o N C C'~N' o (105), \ / \ / H \ I
O
OCZHS
O NHZCHZCHzCH3 0 0 0 (106), N~O C=O I o CH CH CH CH
O(;ZHS O ~ 2 2 2 3 __ N
C O H
i ~ ~ \ / C ~ (107) and ~H C=O
N
H3CH~CHZCH~C O OCZHS
C=O H N
i ~ \ / \ / H ~ I ~ (103).
N C=O
H3CH~CH~CH~C O OOHS
The compounds of formula (1 ) according to the invention are prepared, for example, by reacting 2 mol of compound of formula ~Y~x ~~ CHI (50) which possess an active methylene group -CHI
X --O
or 1 mol of compound of formula (50) and 1 mol of compound of formula R, W (Y,>v /~~CHZ (51 ), which possess an active metllylene group -CHI
O
with 1 mol of one of the compounds of formula O = C3 CH = CH (5~)' ~ (53), R3 R3 (54), C3= O ~ 3 3 O=C- -O=C \g/ C=O W G=O
n Rz Rz i s ~ 3 (55)' O = N CH = CH N = O (56), O=C ~' ~ CH=CH ~' ~ C=O ", Rz (5~), O = N - W - N = O (5$) or O=N ~g~ N=O
n Rz Rz (59), O=N ~ ~ CH=CH ~ / N=O
wherein R~, R~1, X, X~, Y, Y~, Z, Z~, x and y are as defined above for formula (1 ), n is 0, 1, 2 or 3, m is 0, 1, 2 or 3, B is a phenyl ring, RZ is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkyl-thio or amino and R3 is hydrogen, C~-C,zalkyl or CN, at elevated temperature or by oxidation 2 mol of compound of formula (50) at elevated temperature or by oxidation 1 mol of compound of formula (50) and 1 mol of compound of formula (51 ) at elevated temperature.
The general synthesis of phenyl-butyrolactams (in this case C-substituted by carboethoxy) derivatives is characterized by the following reaction schema:
/ (Et0)~CO / CO~Et CICHzCOzEt / ~ COzEt \ ~ CH3 NaOEt \ ~ K.,CO \
i ' Aceton O O O COzEt AcOH / O
N~ \ ~ COZEt [O~ / ~ EtOZC /N
/ \ / / /
HN -~ HN ~ COZEt 5-Phenyl-4-carboethoxy butyrolactam type wherein Ac means acetic acid residue and Et means ethyl.
The general synthesis of phenyl-butyrolactam and phenyl-butyrolactone (N- and C- unsubsti-tuted) derivatives is characterized by the following reaction schema:
/
Ac20 / I
N~ / -\ I \ C02H ~ \
O CuCI
O
O
O O
/I O /I N
\ NCH / CHJ / I ~ \ NCH / CHr / I
O \ HN \
O O
wherein Ac20 means acetic anhydride.
The general synfihesis of phenyl-oxazolone derivatives is characterized by the following reac-tion schema:
AczO /
/ N\
oN
O CO~H
O
Hippurio acid 2-Phenyl-5-oxazolone* O
Heterocycles, 19(12) 2331, 1982 / ~ O
iN / N~ /
O
O O
PhCHzNH
~oH ~ Phenyl-Oxazolone type OH SOCIZ
PhCHZNH
O
wherein Ph means phenyl and Ac20 means acetic anhydride The general synthesis of pheny-imidazolone derivatives is characterized by the following re-action schema:
R~
OOMe COOMe phenyl-imidazolone type wherein R~ has the meaning given under the formula (1 ) and Me is methyl.
The general synthesis based on the condensation of a dialdehyde with an active methylene compound is characterized by the following reaction schema:
OHC'[
/ Y l~I~~\ "cHO / Y
\ iZ / \ X
x x ~ / / ~
O p n Active methylene compound n = o, ~ or 2 Y
wherein X, Y and ~ have the meaning given under the formula (1 ).
The compound of formula (1 ) can be symmetrical or asymmetrical and can contain one or more water soluble groups (sulfonic, carboxylic or cationic groups).
Water soluble derivatives of compounds of formula (1 ) can be used as dyestuffs for textile application, coloration of cotton, wool, polyamide and polyacrylonitrile using all the well known dyeing processes.
Such dyes are useful for dyeing and printing manufactured natural polymer and especially synthetic hydrophobic fibre materials, especially textile materials. Textile materials composed of blend fabrics comprising such manufactured natural polymer or synthetic hydrophobic textile materials are likewise dyeable or printable with the dyes of the invention.
Useful manufactured natural polymer textile materials are especially cellulose acetate and cellulose triacetate.
Synthetic hydrophobic textile materials are especially linear aromatic polyesters, for example polyesters formed from a terephthalic acid and glycols, particularly ethylene glycol, or con-densation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane;
polycarbo-nates, for example those formed from a,oc-dimethyl-4,4-dihydroxydiphenylmethane and phos-gene; or fibres based on polyvinyl chloride or polyamide.
The above dyes are applied to the textile materials according to known dyeing processes.
For example, polyester fibres are exhaust dyed from an aqueous dispersion in the presence of customary anionic or nonionic dispersants with or without customary carriers at temperatu-res between 80 and 140°C. Cellulose acetate is preferably dyed at between about 65 to 85°C
and cellulose triacetate at up to 115°C.
The above dyes are also useful for dyeing by the thermosol, exhaust and continuous proces-ses and for printing processes. The exhaust process is preferred. The liquor ratio depends on the apparatus, the substrate and the make-up form. However, the liquor ratio can be cho-sen to be within a wide range, for example in the range from 4:1 io 100:1, but it preferably is between 6:1 to 25:1.
The textile material mentioned may be present in the various processing forms, for example as a f bre, yarn or web or as a woven or loop-formingly Knitted fabric.
It is advantageous to convert the dyes into a dye preparation before use. For this, the dyes are ground so that their particle size is on average between 0.1 and 10 microns. The grinding may be effected in the presence of dispersants. For example, the dried dye is ground with a dispersant or kneaded in paste form with a dispersant and then dried under reduced pressu-re or by spray drying. The preparations thus obtained can be used to prepare print pastes and dyebaths by adding water.
Printing utilizes the customary thickeners, for example modified or nonmodified natural pro-ducts, for example alginates, British gum, gum arabic, crystal gum, carob bean flour, traga-canth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof or polyvinyl alcohols.
The above dyes confer on the materials mentioned, especially on polyester material, level shades having very good service fastnesses, such as in particular good light fastness, espe-cially a very good hot light fastness, fastness to dry heat setting and pleating, chlorine fast-ness and wet fastness such as fastness to water, perspiration and washing; the dyeings are further characterized by good rub fastness and heat stability.
Water insoluble derivatives of compounds of formula (1 ) can be used as disperse dyes for coloration of PET by exhaustion or pigments for mass coloration of plastics or can be used for inks and paints. These products can also be used for coloration of wood and metals and they are also suitable as functional dyes for special applications such as optical information storage, or display devices or printed circuit boards.
The present invention relates also to a process for the production of coloured plastics or po-lymeric colour particles, which comprises mixing together a high molecular weight organic material and a tinctorially effective amount of afi least one compound of formula (1 ).
The present invention further relates to the use of the compounds of formula (1 ) individually as colourants, especially for colouring or pigmenting organic or inorganic, high-molecular-weight or low-molecular-weight material, especially high-molecular-weight organic material. It is also possible, however, for the compositions according to the invention comprising com-pounds of formula (1 ) to be used in the form of mixtures, solid solutions or mixed crystals.
Compounds of formula (1 ) can also be combined with colourants of another chemical class, for example with dyes or pigments, for example those selected from the group of the diketo-pyrrolopyrroles, quinacridones, perylenes, dioxazines, anthraquinones, indanthrones, fla-vanthrones, indigos, thioindigos, quinophthalones, isoindolinones, isoindolines, phthalocyani-nes, metal complexes, azo pigments and azo dyes.
The high-molecular-weight material may be organic or inorganic and may be synthetic and/or natural material. The high-molecular-weight organic material usually has an average molecu-lar weight of 105-10~g/mol. It may be, for example, a natural resin or a drying oil, rubber or casein or a modified natural material, such as chlorinated rubber, oil-modified alkyd resins, viscose, or a cellulose ether or ester, such as ethylcellulose, cellulose acetate, propionate or butyrate, cellulose acetobutyrate or nitrocellulose, but is especially a completely synthetic or-ganic polymer (duroplasts and thermoplasts) as may be obtained by polymerisation, for example by polycondensation or polyaddition. The class of polymers includes, for example, polyolefins, such as polyethylene, polypropylene, polyisobutylene, and substituted polyole-fins, such as polymerisates of monomers such as vinyl chloride, vinyl acetate, styrene, acry-lonitrile, acrylates, methacrylates, fluoropolymers, such as polyfluoroethylene, polytrifluoro-chloroethylene or tetrafluoroethylene/hexafluoropropylene mixed polymerisate, and copoly-merisates of the mentioned monomers, especially ABS
(acrylonitrile/butadiene/styrene) or EVA (ethylene/vinyl acetate). From the group of polyaddition and polycondensation resins it is possible to use, for example, condensation products of formaldehyde with phenols, the so-called phenoplasts, and condensation products of formaldehyde and urea or thiourea, also melamine, the so-called aminoplasts, and the polyesters used as surface coating resins, either saturated, such as alkyd resins, or unsaturated, such as malefic resins, and also linear polyesters, polyamides, polyurethanes, polycarbonates, polyphenylene oxides or silicones, and silicone resins. The mentioned high-molecular-weight compounds may be present indivi-dually or in mixtures in the form of kneadable compounds, melts or in the form of spinning solutions. They may also be present in the form of their monomers or in the polymerised sta-te in dissolved form as film-formers or binders for paints or printing inks, such as, for examp-le, boiled linseed oil, nitrocellulose, alkyd resins, melamine resins and urea-formaldehyde re-sins or acrylic resins.
Low-molecular-weight materials are, for example, mineral oils, waxes or lubricating greases.
The present invention further relates, theref~re, to the use ~f the c~mpounds ~f formula (1) for the producti~n of inks, for printing inks in printing processes, for flexographic printing, screen printing, the printing of packaging, security colour printing, intaglio printing or offset printing, for preliminary printing stages and for textile printing, for office and home use or for graphics, such as, for example, for paper goods, for ball-point pens, felt-tip pens, fibre-tip pens, paperboard, wood, (wood) stains, metal, stamp pads or inks for impact printing proces-ses (with impact printing ink ribbons), for the production of colourants, for paints, for use in industry or advertising, for textile decoration and industrial labelling, for roll coating or powder coating compositions or for automobile paints, for high-solids (low-solvent), water-containing or metallic paints or for pigmented formulations for aqueous paints, for mineral oils, lubrica-ting greases or waxes, for the production of coloured plastics for coatings, fibres, plates or moulded substrates, for the production of non-impact printing material for digital printing, for the thermal wax-transfer printing process, the ink jet printing process or for the thermal trans-fer printing process, and also for the production of colour filters, especially for visible light in the range of from 400 to 700 nm, for liquid crystal displays (LCDs) or charge-coupled devices (CCDs) or for the production of cosmetics or for the production of polymeric colour particles, toners, dry copy toners, liquid copy toners or electrophotographic toners.
The present invention further relates to inks comprising high-molecular-weight organic mate-rial and a colour-producing amount of the compound of formula (1 ).
For example, the inks can be produced by mixing the compounds according to the invention with polymeric dispersants.
The mixing of the compounds according to the invention with the polymeric dispersant is pre-ferably carried out by generally known mixing methods, such as stirring or mixing, and the use of an intensive mixer, such as an Ultraturax, is especially to be recommended.
When mixing the compounds according to the invention with polymeric dispersants, a water-dilutable organic solvent is advantageously used.
The weight ratio of the compounds according to the invention to ink is advantageously selec-ted to be in the range of from 0.0001 to 75 % by weight, preferably from 0.001 to 50 % by weight, based on the total weight of the ink.
The present inventi~n theref~re relates also to a process f~r the producti~n ~f inks which comprises mixing high-molecular-weight organic material with a colour-producing amount of the compound of formula (1 ).
The present invention further relates to colourants comprising high-molecular-weight organic material and a compound according to the invention of formula (1 ) in a colour-producing amount.
The present invention relates, in addition, to a process for the preparation of colourants which comprises mixing a high-molecular-weight organic material and a colour-producing amount of the compound according to the invention of formula (1 ).
The present invention further relates to coloured or pigmented plastics or polymeric coloured particles comprising high-molecular-weight organic material and compound of formula (1 ) in a colour-producing amount.
The present invention relates, in addition, to a process for the preparation of coloured or pig-mented plastics or polymeric coloured particles which comprises mixing together a high-mo-lecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
The colouring of high-molecular-weight organic substances with the colourants of formula (1 ) is carried out, for example, by mixing such a colourant, optionally in the form of a master batch, into those substrates using roll mills or mixing or grinding apparatus, whereby the co-lourant is dissolved or finely distributed in the high-molecular-weight material. The high-mole-cular-weight organic material with the admixed colourant is then processed according to pro-cedures known per se, such as, for example, calendering, compression moulding, extrusion moulding, coating, spinning, casting or injection-moulding, whereby the coloured material acquires its final form. Admixing of the colourant can also be carried out immediately prior to the actual processing step, for example by continuously metering a powdered colourant ac-cording to the invention and a granulated high-molecular-weight organic material, and option-ally also additional ingredients, such as additives, directly into the inlet gone of an extruder si-multaneously, where mixing takes place just before the processing operation.
In general, however, prior mixing of the colourant into the high-molecular-weight organic material is pre-ferred, since more uniform results can be obtained.
It is often desirable for the purpose of producing non-rigid mouldings or reducing the brittle-ness thereof to incorporate so-called plasticisers into the high-molecular-weight compounds before shaping. There may be used as plasticisers, for example, esters of phosphoric acid, phthalic acid or sebacic acid. In the process according to the invention, the plasticisers can be incorporated into the polymers before or after the incorporation of the colourant. In order to obtain different colour shades it is also possible to add to the high-molecular-weight orga-nic substances, in addition to the compounds of formula (I), any desired amounts of consti-tuents such as white, coloured or black pigments.
For the colouring of paints and printing inks, the high-molecular-weight organic materials and the compounds of formula (1 ) optionally together with additional ingredients, such as fillers, dyes, pigments, siccatives or plasticisers, are finely dispersed or dissolved in a common or-ganic solvent or solvent mixture. That procedure may comprise dispersing or dissolving each individual component on its own or dispersing or dissolving several components together and only then combining all the components. Processing is carried out in accordance with custo-mary methods, for example by spraying, film-spreading or one of the many printing methods, whereupon the paint or printing ink is advantageously cured thermally or by irradiation, optio-nally after previous drying.
When the high-molecular-weight material to be coloured is a paint, it may be a conventional paint or a special paint, for example an automobile finish, preferably a metal-effect finish con-taining, for example, metal or mica particles.
Preference is given to the colouring of thermoplastics, especially also in the form of fibres, and printing inks. Preferred high-molecular-weight organic materials that can be coloured ac-cording to the invention are, very generally, polymers having a dielectric constant >_ 2.5, es-pecially polyesters, polycarbonate (PC), polystyrene (PS), polymethylmethacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or acrylonitrile/butadie-ne/styrene (ABS). More especially preferred are polyesters, polycarbonate, polystyrene and PMMA. Most especially preferred are polyesters, polycarbonate and PMMA, especially aro-matic polyesters that can be obfiained by polycondensation of terephthalic acid, such as, for example, polyethylene terephthalate (PET) or polybutylene terephthalate.
They can be used in the form of their monomers or copolymers or in the polymerised state in dissolved form as film formers or binders for paints that can be used for the decoration of metal or for decorative colour f niches, and for printing inks used, for example, in the ink-jet printing process, or also for wood stains.
Special preference is also given to the colouring of mineral oils, lubricating greases and wa-xes with the compounds according to the invention.
The present invention also relates to mineral oils, lubricating greases and waxes comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
The present invention also relates to a process for the preparation of mineral oils, lubricating greases and waxes, which comprises mixing high-molecular-weight organic material with a colour-producing amount of the compound of formula (1 ).
The present invention also relates to non-impact printing material comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
The present invention relates, in addition, to a process for the preparation of non-impact prin-ting material, which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
The present invention further relates to a process for the production of colour filters compri-sing a transparent substrate and a red, a blue and a green coating applied thereto in any de-sired sequence, which comprises using for the production of the red, blue and green coatings a correspondingly coloured compound of formula (1 ).
The different-coloured coatings are preferably arranged in such a pattern that they do not overlap over at least 5 % of their respective surface area and, most preferably, do not over-lap at all.
The colour filters can be coated, for example, using inks, especially printing inks, comprising the compounds according to the invention, or, for example, by mixing a compound according to the invention witll a chemically, thermally or photolytically structurable high-molecular-weight material (resist). The further production can be carried out, for example, analogously to EP-A-654 711, by application to a substrate, such as an LCD, subsequent photo-structu-ring and developing.
The invention further includes a transparent substrate coated with a red, a blue and a green coating each of a correspondingly coloured compound of formula (1 ), comprising pigmented high-molecular-weight organic material.
The sequence in which coating is carried out is not important as a rule. The different-colou-red coatings are preferably arranged in such a pattern that they do not overlap over at least 5% of their respective surface area and, most preferably, do not overlap at all.
The present invention also includes colour filters comprising a transparent substrate and, applied thereto, a red, a blue and a green coating, each obtainable from a correspondingly coloured compound of formula (1 ).
The present invention also includes the use of the compounds of formula (1 ) for optical infor-mation storage applications (ois).
The present invention relates, in addition, to toners comprising high-molecular-weight organic material and a compound of formula (1), in a colour-producing amount.
The present invention also relates to a process for the production of toners, which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
The present invention also relates to inks or colourants for paints, printing inks, mineral oils, lubricating greases or waxes, or coloured or pigmented plastics, non-impact printing material, colour filters, cosmetics or toners comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
In a special embodiment of the process according to the invention, toners, paints, inks or co-loured plastics are produced by processing master batches of toners, paints, inks or coloured plastics in roil mills or mixing or grinding apparatus.
A colour-producing amount of the compound of formula (1 ) means in the present invention normally from 0.0001 to 99.99 % by weight, preferably from 0.001 to 50 % by weight and es-pecially from 0.01 t~ 50 % by weight, based on the t~tal weight of tile material c~loured or pigmented therewith.
The colouredlpigmented high-molecular-weight materials obtained, such as, for example, plastics, fibres, paints and prints, are distinguished by very high colour intensity, high satura-tion, good fastness to overspraying, good migration-stability, good fastness to heat, light and weathering and by a high gloss and good IR reflectance behaviour.
In order to improve the light fastness properties, UV absorbers are advantageously mixed into the plastics or polymeric particles to be coloured with the compound of formula (1 ) accor-ding to the invention. The amount of UV absorber can vary within a wide range;
advanta-geously there is used from 0.01 to 1.0 % by weight, especially from 0.05 to 0.6 % by weight, more especially from 0.1 to 0.4 % by weight, of a UV absorber, based on the weight of the plastics or polymeric particles.
The following Examples serve to illustrate the invention. Unless otherwise indicated, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres.
Example 1: (general procedure for oxidative dimerization) A solution of 5-phenyl-4-carbethoxy-1,3-dihydro-pyrrol-2-one (10.0 g, 0.04 mol) is heated at 130° C., under stirring in dry DMF (dimethyl formamide) (100 ml). Slow stream of oxygen gas is bubbled through the solution and progress of the reaction is monitored by TLC (~3 hours).
After completion of the reaction, it is poured on water (5-times). Bluish suspension is filtered through Buchner funnel to give dark violet colored crude product (11.0 g). The crude product is purified by selective precipitation from hexane-ethyl acetate solvent mixture to give (2.0 g, 20%) of the pure product. ~H NMR (dmso): ~ 1.1 (6H, t), 4.1 (4H, q), 7.4-7.7 (10H, m), 11.2 (2H, s). All other compounds given in the Table 1 (entries 1, 3, 4, 7) are obtained following the same procedure.
Exa J~le 2: (general procedure for N-butylation) Dimer obtained from process of Example1 (4..5 g, 0.009 mol) is taken in dry DMF (70 ml) under nitrogen atmosphere and the solution is cooled to 5° C. To this sodium hydride 50%
(0.94 g, 0.019 mol) is added in portions. After some time n-butyl bromide (4.65 g, 0.034 mol) is added in cane lot. Reacti~n was monitored by TLC and after the completion, it is poured on brine. Aqueous part is extracted with ethyl acetate, dried over anhydrous sodium sulfate.
Evaporation of organic layer gives the crude violet colored product. It is purified on silica gel column using hexane-ethyl acetate solvent mixture (10 : 90) to give (3.3 g, 58%) of the pure product.'H NMR (dmso): g 0.6(6H, t), 0.8(10H, m), 1.2(4H, t), 3.4(4H, t), 3.9(4H, q), 7.7 (10H, s). All other compounds given in the Table 1 (entries 2, 5, 6) are obtained following the same procedure.
In the following Tables Et means -CH~CHs, Me means -CH3, OMe means -OCH3, t-But means -C(CH3)3, Ph means -Phenyl, OEt means -OCH2CHs and n-But means -(CHZ)3CH3.
Table 1 O
/ Et0 C X
R~ I ZI
\ C / C~ /
X COZEt \ R1 O
Example X R~ Shade (PET) 1 N-H H Violet 2 N-nC4H9 H Violet 3 N-H 4-Me Blue 4 N-H 4-OMe Blue 5 N-nC4H9 4-Me Violet 6 N-nC4H9 4-OMe Violet 7 N-H 4-CI Blue Example 8:
Benzoylacrylic acid (10.Og, 0.056 mol), cuprous chloride (2.0 g, 0.010 mol), ammonium chlo-ride (2,2 g, 0.041 mol) are taken in acetic anhydride (50 ml). It is gradually heated to refilux under stirring for 2 hours. After the reaction is over, it is thoroughly cooled in an ice bath.
Settled solids are filtered through Buchner funnel. Solids are washed with acetic anhydride, water and ethanol to give the crude product (5.2 g). The crude solids are purifiied by soxhlet extraction in toluene to give pure red colored s~lids (3.8 g, 42%). m.
p.315°C, Anal. Calc. For C2oH~aOa; C. 75.94; H, 3.82; Found: C, 74.79; H, 3.82. All other compounds given in the Table 2 are obtained following the above same procedure.
Table 2 O
/ O
R~
i H /
CH /
O R~
O
Example R1 Shade (PET) 8 H Scarlet (fluorescent) 9 4-Me Red 4-t-But Red 11 4-Ph Red 12 4-OMe Red 13 4-O Et Red 14 4-CI Red 4-Br Red 16 3-NO2 Red Example 17:
2.0 g of the above dimmer from Example 8 is taken in acetic acid (50 ml).
Ammonia gas is then bubbled through the solution under reflux for 2 hours. Reaction mixture is cooled to 70° C. and filtered. Solids are washed with water, ethanol and ether.
The crude product is purified by continuous soxhlet extraction to give (1.4 g, 70%) of violet colored product. Anal.
Calc. For CzoH~aN~02; C, 76.42; H, 4.49; N, 8.90; Found: C, 75.84; H, 5.10 ;
N, 7.70. All other compounds given in the Table 3 are obtained following the above same procedure.
Table 3 ~ H
N, R~
CH / CHr /
H \ R~
H
Example R~ Shade (PET) 17 H Violet 18 4-Me Violet 19 4-t-But Violet 4-Ph Violet 21 4-OMe Grey 22 4-OEt Grey 23 4-CI Red 24 4-Br Red 3-NO2 Red Example 26:
2,3-Bis-benzoylamino-succinic acid (5.0 g, 0.014 mol) (synthesized as given in Stachel, S. D.
et al. Arch. Pharm. 312, 968, 1979) is taken in thionyl chloride (50 ml) and refluxed for 2 hours. Excess thionyl chloride is distilled off. Traces of thionyl chloride are removed by tolue-ne co-distillation. It is cooled to room temperature and water is added to it.
The crude mass is then filtered and dried in an oven till constant weight. The red colored pure product obtained, weighted (3.5g, 78%). Anal. Calc. For C~$H~oN~04; C, 67.90; H, 3.17; N, 8.8;
Found: C, 67.07; H, 4.95 ; N, 8.81. All other compounds given in the Table 4 are obtained following the above same procedure.
Table 4 R~
\ N / Ni /
R~
Example R~ Shade (PET) 2G H Red 27 4-Me Red 28 4-CI Red 29 4~-N~2 Red Example 30:
Benzamidine free base (6.0 g, 0.049 mol) and dimethyl acetylenedicarboxylate (3.6 g, 0.025 mol) are taken in benzene (ca. 50 ml). The deep red colored solution obtained is heated to reflux for 2 hours. The cooled mixture is filtered to give (9.0 g) of the crude. The crude pro-duct is taken in minimum amount of warm DMF and poured on large excess of water under stirring. The solids separated (2.1 g) are filtered and soxhlet extracted with methanol for 16 hours. The methanol insoluble pure red colored product obtained, weighted (0.8 g, 10%).
Anal. Calc. For C~gH~2N4O2; C, 68.37; H, 3.79; N, 17.72; Found: C, 69.33; H, 3.43 ; N, 17.47.
Methoxy derivative from Example 31 (see Table 5) is synthesized using above same method.
Table 5 O H
/ N.
\ N / N~ /
N \ R~
H~ O
Example R, Shade (PET) 30 H Yellow 31 4-OMe Orange Example 33:
5-Phenyl-4-carbethoxy-1,3-dihydro-pyrrol-2-one (2.3 g, 0.01 mol) is dissolved in acetic acid (50 ml) at 60 to 70° C. To this PTSA (0.7 g) is added, followed by addition of 2,5-dimethoxy-terephthalaldehyde (1.0 g, 0.005 mol) and temperature is increased to 100° C. Heating is continued for 3 hours and after cooling, solids are filtered through Buchner funnel. The crude product is washed with acetic said, water, DMF and methanol. Finally the crude product is dissolved in cone. sulphuric acid, reprecipitated from water and filtered. It is then dried in an oven to give red colored pure product (1.5 g, 50%). Anal. Calc. For C36H3~N2Oa, C, 69.60; H, 5.15; N, 4.52; Found: G, 66.47; H, 4.98 ; N, 4.34. All other compounds given in the Table 6 are obtained following the above same procedure Table G
/ CO2Et RZ
C O H
/ \ N.
N
O ~n ' C \
I I R~
Rz COZEt /
Example n R~ Rz Shade (PET) 32 0 H H Red 33 1 H OMe Orange 34 1 H H Orange 35 2 H H Yellow 36 0 4-Me H Red 37 1 4-Me H Orange 38 2 4-Me H Yellow 39 0 4-CI H Red 40 1 4-CI H Orange 41 2 4-CI H Yellow 42 0 4-OMe H Red 43 1 4-OMe H Orange Example 44:
5-(p-Methylphenyl)-4-carbethoxy-1,3-dihydro-pyrrol-2-one (5.1 g, 0.0086 mol) is taken in dry DMF (70 ml) under nitrogen atmosphere and the solution is cooled to 5°
C. To this sodium hydride 50% (1.0 g, 0.04 mol) is added in portions. After some time n-butyl bromide (6.35 g, 0.046 mol) is added to it at ones. Reaction is monitored by TLC and after the completion, it is poured on brine. Aqueous part is extracted with ethylacetate, dried over anhydrous sodium sulfate. Evaporation of organic layer gives the crude violet colored product.
It is purified on si-lica gel column using hexane-ethyl acetate solvent mixture (10 : 90) to give (3.5 g,58%) of the pure product.'H NMR (dmso): 5 0.6(6H, t), 0.8(6H, t), 1.2(4H, m), 1.4(4H, m), 2.4(6H, s),3.4(4H, t), 4.0(4H, q), 7.2-8.3(14H, m). All other compounds given in the Table 7 are obtai-ned following the same procedure.
Table 7 R / COZEt R' O ,nBut i / ~ N
N L I / /
nBut~ ~ .
RZ CO2Et / R~
Example n R, R~ Shade (PET) 44 1 4-Me H Gold Yellow 45 1 H H Orange 46 2 H H Yellow 47 0 4-Me H Red 48 0 H H Red 49 2 4-Me H Yellow 50 0 4-CI H Red 51 1 4-CI H Orange 52 2 4-CI H Yellow 53 1 4-OMe H Red Example 54:
Terephthalaldehyde (2.0 g, 0.015 mol), sodium acetate (7.5 g, 0.091 mol) and acetic anhydri-de (70 ml) are taken in round bottom flask and heated to 90° C under nitrogen atmosphere.
To this is added (3-Benzoylpropionic acid (16.0 g, 0.09 mol). Temperature of the reaction is maintained for 3 hours and after cooling solids are filtered through Buchner funnel, washed with acetic acid, water and methanol. The crude product is heated in DMF at 80-90° C for 2 hours. After filtration and washing with water, it is dried in an oven till constant weight to give (5.2g, 83%) of the pure product. Anal. Calc. For Cz$H,$O4; C, 78.37; H, 4.34;
Found: C, 78.87; H, 4.45. The compounds of Examples 55 and 56 (see table 8) are synthesized using above same method.
Table 8 / R
R z O
~ \ iCH / \ O
O L ~ / /
~ ~ 'CH
R~
Rz /
Example n R~ Rz Shade (PET) 54 1 H H Orange 55 1 H OMe Orange 56 2 H H Yellow Example 57:
Above prepared lactone of Example 54 (11.5 g, 0.027 mol) is taken in acetic acid (200 ml).
Ammonia gas is bubbled through it and the solution is refluxed for 2 hours.
After completion of the reaction, it is cooled and filtered. The solids are washed with acetic acid, water and methanol. Final purification is done by stirring the solids in DMF at room temperature for 4-5 hours. Filtered solids are then washed with water, methanol and dried in an oven till constant weight to give (10.2 g, 89%) of the orange colored pure product. Anal. Calc.
For C~$HzoNz02;
C, 80.76; H, 4.80;N, 6.73 Found: C, 80.37; H, 4.14; N, 7.21. Example 58 (see Table 9) is synthesized using above same method.
Example 59:
Above lactam from Example 57 (6.5 g, 0.020 mol) is taken in dry DMF (90 ml) under nitrogen atmosphere and the solution is cooled to 5° C. To this sodium hydride 50% (1.8 g, 0.075 mol) is added in portions. After some time n-butyl bromide (9.90 g, 0.075 mol) is added to it at ones. Reaction is monitored by TLC and after completion, it is poured on brine. Aqueous part is extracted with ethyl acetate, dried over anhydrous sodium sulfate.
Evaporation of or-ganic layer gives the crude orange colored product. It is purified on silica gel column using hexane-ethyl acetate solvent mixture (10 : 90) to give orange colored (2.0 g,18%) of the pure product. m. p. 160°C; ~H NMR (cdcls): ~ 0.8(6H, t), 1.2(4H, t), 1.4(4H, m), 3.7(4H, t), 6.2(2H, s), 7.2-7.6(16H, m).
Table 9 / R
R
\ X
X / / ~ \
~ ~ CH
R~
R~ /
Example X n R~ Rz Shade (PET) 57 NH 1 H H Orange 58 NH 2 H H Yellow 59 N-nBut1 H H ~range Example 60:
Terephthalaldehyde (7.0 g, 0.055 mol), sodium acetate (14 g, 0.017 mol) and acetic anhydri-de (150 ml) are taken in round bottom flask and heated to 90° C under nitrogen atmosphere.
To this is added hippuric acid (30.0 g, 0.167 mol). Temperature of the reaction is maintained for 4 hours and after cooling yellow solids are filtered through Buchner funnel, washed with acetic acid, water and methanol. The crude product is heated in DMF at 80-90° C for 2 hours. After filtration and washing with water, it is dried in an oven till constant weight to give (14.5g, 66%) of the pure product. Anal. Calc. For C~sH~6Na04; C, 74.28; H, 3.84;N, 6.66 Found: C, 73.57; H, 3.67; N, 6.79.
Table 10 / ~ R
R z O
1 \ ~N / \ O
O ~I / /
O )n ~ N I \
R~
R~ /
Example n R~ R2 Shade (PET) 60 1 H H Yellow (fluorescent) 61 0 H H Orange 62 2 H H Yellow Example 63:
Above oxazoline based compound of Example 61 (1.0 g, 0.0023 mole) is taken in acetic acid (30 ml). The reaction mixture is refluxed while ammonia gas is bubbled through the solution for 2 hours. The reaction mixture is filtered after cooling and washed with acetic acid, water and methanol. The crude mass is stirred in DMF at room temperature for 15 hours followed by boiling in water f~r 3 hours. Final wash is given with methanol and dried in an oven till constant weight. The pure product obfiained in this way gives (2.5 g, 22%) yield of the pure product. Anal. Calc. For G2~H,gN402; C, 74.64; H, 4.34;N, 13.79 Found: C, 72.75; H, 4.19; N, 13.60.
Table 11 / R
R ~ O
iN / \ N -H
H- N ~ I / /
O .~ ' N I \
R~
R~ /
Example n R~ R2 Shade (PET) 63 1 H H Orange 64 2 H H Yellow Dyeing Example 1:
1200.00 g of polyester granules (PET Arnite D04-300, DSM) are pre-dried for 4 hours at 130°C and then mixed homogeneously with 2.6 g of the compound of formula i C i ~ ~ (100) O H
O
in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute.
The homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin, D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 275°C, cooled with water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) and then dried for 4 hours at 130°C.
The resulting greenish yellow-coloured polyester granules have good allround fastness pro-perties, especially good light fastness and high-temperature light fastness properties.
Dyeing Example 2:
1200.00 g of polyamide-6 granules (lJltramid 831, BASF) are pre-dried for 4 hours at 75°C
and then mixed homogeneously with 3.5 g of the compound of formula OC H ~ ~HaOHZCHZGH3 z s C ~ H i /
i ~ \ / H I ~ (108) C=O
1 O Oc2H5 H3CHzCHzCHzC
in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute.
The homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin, D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 220°C, cooled with water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) and then dried for 4 hours at 75°C.
The resulting orange-coloured polyamide granules have good allround fastness properties, especially good light fastness and high-temperature light fastness properties.
THEIR USE AS DYES AND PIGMENTS
The present invention relates to new compounds, to their preparation and to their use in the production of coloured plastics or polymeric colour particles.
The subject of the present invention are compounds of formula (1) O
X' R~
Z A Z' ~ (1), I R'~
X ~Y~)v ~
O
wherein R~ is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, Garb~xylic ester, sulfo, sulfo-nic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, R', is hydrogen, Ilydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfo-nic ester, carboxylic amide, sulfonic amide, alkyltllio, arylthio, alkoxy or aryloxy, X is -O-, -S-, -NH- or-N(alkyl)-, X' is -O-, -S-, -NH- or-N(alkyl)-, Y is hydrogen or carboxylic .ester, Y' is hydrogen or Garb~xylic ester, Z is =C- or =N-, Z' is =C- or =N-, x is 0 or 1, when Z is =N-, then x is 0, y is 0 or 1, when Z' is =N-, then y is 0, A is a conjugated linking bridge of the formula Rz T
j , ~T.~ /~ / , ~ g /TAW / or L" JrriT I / / ' vT/
JnT/
Rz Rz iT ~~/ G G ~ / Ti, wherein n is 0, 1, 2 or 3, m is 0, 1, 2 or 3, B is a phenyl ring, T is =C(R3)- or =N-, wherein R3 is hydrogen, C~-C~2alkyl or CN, W is a heterocyclic, or linear or polycondensed aromatic group which is unsubstituted or sub-stituted by alkyl, halogen, hydroxy, alkoxy, alkylthio or amino, G is -CH= or-N=, and Rz is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino.
According to the invention an alkyl is for example a straight-chain or branched C~_$alkyl as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl or octyl, prefe-rence being given to a C,_4alkyl.
According to the invention an alkylthio is for example methylthio, ethylthio, propylthio, butyl-tllio, lleptylthio or hexylthio.
According to the invention an alkoxy is for example a straight-chain or branched C,_$alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.
butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1,1,3,3-tetramethylbutoxy or 2-ethylhexyloxy.
According to the invention an aryloxy is to be understood as being for example a C6_~øaryl-oxy, preferably a C6_~~arylOxy radical, for example phenoxy or 4-methylphenoxy.
According to the invention an arylthio is for example phenylthio or napthylthio.
G is preferred -CH=.
W as aromatic group includes, for example, phenylene, naphthalene, acenaphthylene, anthracene, phenanthrene, naphthacene, chrysene, pyrene or perylene. W is preferably phe-nylene, naphthalene, anthracene, phenanthrene, perylene or pyrene, and most preferably phenylene or naphthalene.
W as heterocyclic group is, for instance, pyridine, pyrazine, pyrimidine, pyridazine, indole iso-indole, quinoline, isoquinoline, carbazole, phenothiazine, benzimidazolone, benzothiazole, pyrrolo, imidazole, pyrrolidine, piperidine, piperazine, morpholine or pyrazole.
According to the invention an ester is for example methyl-, ethyl-, propyl- or butylester.
If A is a single double bond / , preferred compounds of formula (1 ) are a) compounds of phenyl-butyrolactams of formula / ~ EtOZC N -H / H N -H
i /
R1 \ C C/ / , R1 \ ~ / C~ / and H- N CO Et \ R1 I R1 z H- N H \
~ O
O
R / ~ EtOZC N -nC4H9 ~ \ C / Ci /
H9CQn- N COzEt \
O
b) compounds of phenyl-butyrolactones of formula O
/ H O
\ ~ / O~ / , O H \
O
c) compounds of phenyl oxazolones of formula O
O
\ N / Ni O \ H1 O
and d) compounds of phenyl imidazolones of formula O
/ ~ N -H
R~
\ N / Ni /
R~
H- N \
O
wherein R, has the meaning given under the formula (1 ) and Et is -CH2CH3.
If A is a conjugated linking bridge, preferred compounds of formula (1 ) are e) compounds of phenyl-carboethoxy-butyrolactams of formula / CO~Et RZ
R ~ ~ O H
\ N, and N
H, ~ n C \
R~ C~~Et ~ / R1 n=0, 1 or2 / COZEt R~
R ~ I O nBut \ N.
N /
nBllt~~ O n ~ \
_. ~ _ _. ~ R~
f) compounds of phenyl-butyrolactones of formula R / ~ H R~
~c / ~ \ o o / r Q n C \
I I R~
RZ H /
n=0, 1 or2 n=0, 1 or2 ~g) compounds of phenyl-butyrolactams of formula \ C
N-H O ~ J n" ~j I I ~ R1 h) compounds of phenyl-oxazolones of formula / R
R z O
1 \ iN / \ O
O L I / /
O ~ 'N \
Rz I /
n=0, 1 or2 and i) compounds of phenyl-imidazolones ~f formula R
R1 \ I N z O H
/ \ N.
N I / /
H, O ~ , N I \
n=0, 1 or2 wherein R1 and R2 have the meaning given under the formula (1 ), Et is -CHzCH3 and nEut is n-butanole.
Further preferred are compounds of formula (1 ), wherein R1 is hydrogen, chloro, bromo, methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro is, R~1 is hydrogen, chloro, bromo, methyl, methoxy, ethoxy, tert.-butyl, , phenyl or nitro, RZ is hydrogen or methoxy, X is -NH-, -N(n-C4H9)-, or -O-, X is -NH-, -N(n-C4H9)-, or -O-, Y is hydrogen or COOCzHS, Y is hydro-gen or COOC2H5, Z is =C- or =N-, Z~ is =C- or =N-, A is = or -T ~ g ~ T = , n T is =C(R3)-, R3 is hydrogen and n is 0, 1 or 2.
n=0, 1 or2 The most preferred compounds of formula (1) are the compounds of the formulae O
I o C o C~ , (100), o H wl I o C C ~~~ o (101 ), ' ' \ / H H ~
O
I o C C C~~ o (102), ~H H ~
O
O
O
I o N C C~~ o (103), / H
O- ~ w O
O
O
I o C C Ci\C' o (104), ' \ / \ / H H
O
O
O
O
I o N C C'~N' o (105), \ / \ / H \ I
O
OCZHS
O NHZCHZCHzCH3 0 0 0 (106), N~O C=O I o CH CH CH CH
O(;ZHS O ~ 2 2 2 3 __ N
C O H
i ~ ~ \ / C ~ (107) and ~H C=O
N
H3CH~CHZCH~C O OCZHS
C=O H N
i ~ \ / \ / H ~ I ~ (103).
N C=O
H3CH~CH~CH~C O OOHS
The compounds of formula (1 ) according to the invention are prepared, for example, by reacting 2 mol of compound of formula ~Y~x ~~ CHI (50) which possess an active methylene group -CHI
X --O
or 1 mol of compound of formula (50) and 1 mol of compound of formula R, W (Y,>v /~~CHZ (51 ), which possess an active metllylene group -CHI
O
with 1 mol of one of the compounds of formula O = C3 CH = CH (5~)' ~ (53), R3 R3 (54), C3= O ~ 3 3 O=C- -O=C \g/ C=O W G=O
n Rz Rz i s ~ 3 (55)' O = N CH = CH N = O (56), O=C ~' ~ CH=CH ~' ~ C=O ", Rz (5~), O = N - W - N = O (5$) or O=N ~g~ N=O
n Rz Rz (59), O=N ~ ~ CH=CH ~ / N=O
wherein R~, R~1, X, X~, Y, Y~, Z, Z~, x and y are as defined above for formula (1 ), n is 0, 1, 2 or 3, m is 0, 1, 2 or 3, B is a phenyl ring, RZ is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkyl-thio or amino and R3 is hydrogen, C~-C,zalkyl or CN, at elevated temperature or by oxidation 2 mol of compound of formula (50) at elevated temperature or by oxidation 1 mol of compound of formula (50) and 1 mol of compound of formula (51 ) at elevated temperature.
The general synthesis of phenyl-butyrolactams (in this case C-substituted by carboethoxy) derivatives is characterized by the following reaction schema:
/ (Et0)~CO / CO~Et CICHzCOzEt / ~ COzEt \ ~ CH3 NaOEt \ ~ K.,CO \
i ' Aceton O O O COzEt AcOH / O
N~ \ ~ COZEt [O~ / ~ EtOZC /N
/ \ / / /
HN -~ HN ~ COZEt 5-Phenyl-4-carboethoxy butyrolactam type wherein Ac means acetic acid residue and Et means ethyl.
The general synthesis of phenyl-butyrolactam and phenyl-butyrolactone (N- and C- unsubsti-tuted) derivatives is characterized by the following reaction schema:
/
Ac20 / I
N~ / -\ I \ C02H ~ \
O CuCI
O
O
O O
/I O /I N
\ NCH / CHJ / I ~ \ NCH / CHr / I
O \ HN \
O O
wherein Ac20 means acetic anhydride.
The general synfihesis of phenyl-oxazolone derivatives is characterized by the following reac-tion schema:
AczO /
/ N\
oN
O CO~H
O
Hippurio acid 2-Phenyl-5-oxazolone* O
Heterocycles, 19(12) 2331, 1982 / ~ O
iN / N~ /
O
O O
PhCHzNH
~oH ~ Phenyl-Oxazolone type OH SOCIZ
PhCHZNH
O
wherein Ph means phenyl and Ac20 means acetic anhydride The general synthesis of pheny-imidazolone derivatives is characterized by the following re-action schema:
R~
OOMe COOMe phenyl-imidazolone type wherein R~ has the meaning given under the formula (1 ) and Me is methyl.
The general synthesis based on the condensation of a dialdehyde with an active methylene compound is characterized by the following reaction schema:
OHC'[
/ Y l~I~~\ "cHO / Y
\ iZ / \ X
x x ~ / / ~
O p n Active methylene compound n = o, ~ or 2 Y
wherein X, Y and ~ have the meaning given under the formula (1 ).
The compound of formula (1 ) can be symmetrical or asymmetrical and can contain one or more water soluble groups (sulfonic, carboxylic or cationic groups).
Water soluble derivatives of compounds of formula (1 ) can be used as dyestuffs for textile application, coloration of cotton, wool, polyamide and polyacrylonitrile using all the well known dyeing processes.
Such dyes are useful for dyeing and printing manufactured natural polymer and especially synthetic hydrophobic fibre materials, especially textile materials. Textile materials composed of blend fabrics comprising such manufactured natural polymer or synthetic hydrophobic textile materials are likewise dyeable or printable with the dyes of the invention.
Useful manufactured natural polymer textile materials are especially cellulose acetate and cellulose triacetate.
Synthetic hydrophobic textile materials are especially linear aromatic polyesters, for example polyesters formed from a terephthalic acid and glycols, particularly ethylene glycol, or con-densation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane;
polycarbo-nates, for example those formed from a,oc-dimethyl-4,4-dihydroxydiphenylmethane and phos-gene; or fibres based on polyvinyl chloride or polyamide.
The above dyes are applied to the textile materials according to known dyeing processes.
For example, polyester fibres are exhaust dyed from an aqueous dispersion in the presence of customary anionic or nonionic dispersants with or without customary carriers at temperatu-res between 80 and 140°C. Cellulose acetate is preferably dyed at between about 65 to 85°C
and cellulose triacetate at up to 115°C.
The above dyes are also useful for dyeing by the thermosol, exhaust and continuous proces-ses and for printing processes. The exhaust process is preferred. The liquor ratio depends on the apparatus, the substrate and the make-up form. However, the liquor ratio can be cho-sen to be within a wide range, for example in the range from 4:1 io 100:1, but it preferably is between 6:1 to 25:1.
The textile material mentioned may be present in the various processing forms, for example as a f bre, yarn or web or as a woven or loop-formingly Knitted fabric.
It is advantageous to convert the dyes into a dye preparation before use. For this, the dyes are ground so that their particle size is on average between 0.1 and 10 microns. The grinding may be effected in the presence of dispersants. For example, the dried dye is ground with a dispersant or kneaded in paste form with a dispersant and then dried under reduced pressu-re or by spray drying. The preparations thus obtained can be used to prepare print pastes and dyebaths by adding water.
Printing utilizes the customary thickeners, for example modified or nonmodified natural pro-ducts, for example alginates, British gum, gum arabic, crystal gum, carob bean flour, traga-canth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof or polyvinyl alcohols.
The above dyes confer on the materials mentioned, especially on polyester material, level shades having very good service fastnesses, such as in particular good light fastness, espe-cially a very good hot light fastness, fastness to dry heat setting and pleating, chlorine fast-ness and wet fastness such as fastness to water, perspiration and washing; the dyeings are further characterized by good rub fastness and heat stability.
Water insoluble derivatives of compounds of formula (1 ) can be used as disperse dyes for coloration of PET by exhaustion or pigments for mass coloration of plastics or can be used for inks and paints. These products can also be used for coloration of wood and metals and they are also suitable as functional dyes for special applications such as optical information storage, or display devices or printed circuit boards.
The present invention relates also to a process for the production of coloured plastics or po-lymeric colour particles, which comprises mixing together a high molecular weight organic material and a tinctorially effective amount of afi least one compound of formula (1 ).
The present invention further relates to the use of the compounds of formula (1 ) individually as colourants, especially for colouring or pigmenting organic or inorganic, high-molecular-weight or low-molecular-weight material, especially high-molecular-weight organic material. It is also possible, however, for the compositions according to the invention comprising com-pounds of formula (1 ) to be used in the form of mixtures, solid solutions or mixed crystals.
Compounds of formula (1 ) can also be combined with colourants of another chemical class, for example with dyes or pigments, for example those selected from the group of the diketo-pyrrolopyrroles, quinacridones, perylenes, dioxazines, anthraquinones, indanthrones, fla-vanthrones, indigos, thioindigos, quinophthalones, isoindolinones, isoindolines, phthalocyani-nes, metal complexes, azo pigments and azo dyes.
The high-molecular-weight material may be organic or inorganic and may be synthetic and/or natural material. The high-molecular-weight organic material usually has an average molecu-lar weight of 105-10~g/mol. It may be, for example, a natural resin or a drying oil, rubber or casein or a modified natural material, such as chlorinated rubber, oil-modified alkyd resins, viscose, or a cellulose ether or ester, such as ethylcellulose, cellulose acetate, propionate or butyrate, cellulose acetobutyrate or nitrocellulose, but is especially a completely synthetic or-ganic polymer (duroplasts and thermoplasts) as may be obtained by polymerisation, for example by polycondensation or polyaddition. The class of polymers includes, for example, polyolefins, such as polyethylene, polypropylene, polyisobutylene, and substituted polyole-fins, such as polymerisates of monomers such as vinyl chloride, vinyl acetate, styrene, acry-lonitrile, acrylates, methacrylates, fluoropolymers, such as polyfluoroethylene, polytrifluoro-chloroethylene or tetrafluoroethylene/hexafluoropropylene mixed polymerisate, and copoly-merisates of the mentioned monomers, especially ABS
(acrylonitrile/butadiene/styrene) or EVA (ethylene/vinyl acetate). From the group of polyaddition and polycondensation resins it is possible to use, for example, condensation products of formaldehyde with phenols, the so-called phenoplasts, and condensation products of formaldehyde and urea or thiourea, also melamine, the so-called aminoplasts, and the polyesters used as surface coating resins, either saturated, such as alkyd resins, or unsaturated, such as malefic resins, and also linear polyesters, polyamides, polyurethanes, polycarbonates, polyphenylene oxides or silicones, and silicone resins. The mentioned high-molecular-weight compounds may be present indivi-dually or in mixtures in the form of kneadable compounds, melts or in the form of spinning solutions. They may also be present in the form of their monomers or in the polymerised sta-te in dissolved form as film-formers or binders for paints or printing inks, such as, for examp-le, boiled linseed oil, nitrocellulose, alkyd resins, melamine resins and urea-formaldehyde re-sins or acrylic resins.
Low-molecular-weight materials are, for example, mineral oils, waxes or lubricating greases.
The present invention further relates, theref~re, to the use ~f the c~mpounds ~f formula (1) for the producti~n of inks, for printing inks in printing processes, for flexographic printing, screen printing, the printing of packaging, security colour printing, intaglio printing or offset printing, for preliminary printing stages and for textile printing, for office and home use or for graphics, such as, for example, for paper goods, for ball-point pens, felt-tip pens, fibre-tip pens, paperboard, wood, (wood) stains, metal, stamp pads or inks for impact printing proces-ses (with impact printing ink ribbons), for the production of colourants, for paints, for use in industry or advertising, for textile decoration and industrial labelling, for roll coating or powder coating compositions or for automobile paints, for high-solids (low-solvent), water-containing or metallic paints or for pigmented formulations for aqueous paints, for mineral oils, lubrica-ting greases or waxes, for the production of coloured plastics for coatings, fibres, plates or moulded substrates, for the production of non-impact printing material for digital printing, for the thermal wax-transfer printing process, the ink jet printing process or for the thermal trans-fer printing process, and also for the production of colour filters, especially for visible light in the range of from 400 to 700 nm, for liquid crystal displays (LCDs) or charge-coupled devices (CCDs) or for the production of cosmetics or for the production of polymeric colour particles, toners, dry copy toners, liquid copy toners or electrophotographic toners.
The present invention further relates to inks comprising high-molecular-weight organic mate-rial and a colour-producing amount of the compound of formula (1 ).
For example, the inks can be produced by mixing the compounds according to the invention with polymeric dispersants.
The mixing of the compounds according to the invention with the polymeric dispersant is pre-ferably carried out by generally known mixing methods, such as stirring or mixing, and the use of an intensive mixer, such as an Ultraturax, is especially to be recommended.
When mixing the compounds according to the invention with polymeric dispersants, a water-dilutable organic solvent is advantageously used.
The weight ratio of the compounds according to the invention to ink is advantageously selec-ted to be in the range of from 0.0001 to 75 % by weight, preferably from 0.001 to 50 % by weight, based on the total weight of the ink.
The present inventi~n theref~re relates also to a process f~r the producti~n ~f inks which comprises mixing high-molecular-weight organic material with a colour-producing amount of the compound of formula (1 ).
The present invention further relates to colourants comprising high-molecular-weight organic material and a compound according to the invention of formula (1 ) in a colour-producing amount.
The present invention relates, in addition, to a process for the preparation of colourants which comprises mixing a high-molecular-weight organic material and a colour-producing amount of the compound according to the invention of formula (1 ).
The present invention further relates to coloured or pigmented plastics or polymeric coloured particles comprising high-molecular-weight organic material and compound of formula (1 ) in a colour-producing amount.
The present invention relates, in addition, to a process for the preparation of coloured or pig-mented plastics or polymeric coloured particles which comprises mixing together a high-mo-lecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
The colouring of high-molecular-weight organic substances with the colourants of formula (1 ) is carried out, for example, by mixing such a colourant, optionally in the form of a master batch, into those substrates using roll mills or mixing or grinding apparatus, whereby the co-lourant is dissolved or finely distributed in the high-molecular-weight material. The high-mole-cular-weight organic material with the admixed colourant is then processed according to pro-cedures known per se, such as, for example, calendering, compression moulding, extrusion moulding, coating, spinning, casting or injection-moulding, whereby the coloured material acquires its final form. Admixing of the colourant can also be carried out immediately prior to the actual processing step, for example by continuously metering a powdered colourant ac-cording to the invention and a granulated high-molecular-weight organic material, and option-ally also additional ingredients, such as additives, directly into the inlet gone of an extruder si-multaneously, where mixing takes place just before the processing operation.
In general, however, prior mixing of the colourant into the high-molecular-weight organic material is pre-ferred, since more uniform results can be obtained.
It is often desirable for the purpose of producing non-rigid mouldings or reducing the brittle-ness thereof to incorporate so-called plasticisers into the high-molecular-weight compounds before shaping. There may be used as plasticisers, for example, esters of phosphoric acid, phthalic acid or sebacic acid. In the process according to the invention, the plasticisers can be incorporated into the polymers before or after the incorporation of the colourant. In order to obtain different colour shades it is also possible to add to the high-molecular-weight orga-nic substances, in addition to the compounds of formula (I), any desired amounts of consti-tuents such as white, coloured or black pigments.
For the colouring of paints and printing inks, the high-molecular-weight organic materials and the compounds of formula (1 ) optionally together with additional ingredients, such as fillers, dyes, pigments, siccatives or plasticisers, are finely dispersed or dissolved in a common or-ganic solvent or solvent mixture. That procedure may comprise dispersing or dissolving each individual component on its own or dispersing or dissolving several components together and only then combining all the components. Processing is carried out in accordance with custo-mary methods, for example by spraying, film-spreading or one of the many printing methods, whereupon the paint or printing ink is advantageously cured thermally or by irradiation, optio-nally after previous drying.
When the high-molecular-weight material to be coloured is a paint, it may be a conventional paint or a special paint, for example an automobile finish, preferably a metal-effect finish con-taining, for example, metal or mica particles.
Preference is given to the colouring of thermoplastics, especially also in the form of fibres, and printing inks. Preferred high-molecular-weight organic materials that can be coloured ac-cording to the invention are, very generally, polymers having a dielectric constant >_ 2.5, es-pecially polyesters, polycarbonate (PC), polystyrene (PS), polymethylmethacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or acrylonitrile/butadie-ne/styrene (ABS). More especially preferred are polyesters, polycarbonate, polystyrene and PMMA. Most especially preferred are polyesters, polycarbonate and PMMA, especially aro-matic polyesters that can be obfiained by polycondensation of terephthalic acid, such as, for example, polyethylene terephthalate (PET) or polybutylene terephthalate.
They can be used in the form of their monomers or copolymers or in the polymerised state in dissolved form as film formers or binders for paints that can be used for the decoration of metal or for decorative colour f niches, and for printing inks used, for example, in the ink-jet printing process, or also for wood stains.
Special preference is also given to the colouring of mineral oils, lubricating greases and wa-xes with the compounds according to the invention.
The present invention also relates to mineral oils, lubricating greases and waxes comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
The present invention also relates to a process for the preparation of mineral oils, lubricating greases and waxes, which comprises mixing high-molecular-weight organic material with a colour-producing amount of the compound of formula (1 ).
The present invention also relates to non-impact printing material comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
The present invention relates, in addition, to a process for the preparation of non-impact prin-ting material, which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
The present invention further relates to a process for the production of colour filters compri-sing a transparent substrate and a red, a blue and a green coating applied thereto in any de-sired sequence, which comprises using for the production of the red, blue and green coatings a correspondingly coloured compound of formula (1 ).
The different-coloured coatings are preferably arranged in such a pattern that they do not overlap over at least 5 % of their respective surface area and, most preferably, do not over-lap at all.
The colour filters can be coated, for example, using inks, especially printing inks, comprising the compounds according to the invention, or, for example, by mixing a compound according to the invention witll a chemically, thermally or photolytically structurable high-molecular-weight material (resist). The further production can be carried out, for example, analogously to EP-A-654 711, by application to a substrate, such as an LCD, subsequent photo-structu-ring and developing.
The invention further includes a transparent substrate coated with a red, a blue and a green coating each of a correspondingly coloured compound of formula (1 ), comprising pigmented high-molecular-weight organic material.
The sequence in which coating is carried out is not important as a rule. The different-colou-red coatings are preferably arranged in such a pattern that they do not overlap over at least 5% of their respective surface area and, most preferably, do not overlap at all.
The present invention also includes colour filters comprising a transparent substrate and, applied thereto, a red, a blue and a green coating, each obtainable from a correspondingly coloured compound of formula (1 ).
The present invention also includes the use of the compounds of formula (1 ) for optical infor-mation storage applications (ois).
The present invention relates, in addition, to toners comprising high-molecular-weight organic material and a compound of formula (1), in a colour-producing amount.
The present invention also relates to a process for the production of toners, which comprises mixing together a high-molecular-weight organic material and a colour-producing amount of the compound of formula (1 ).
The present invention also relates to inks or colourants for paints, printing inks, mineral oils, lubricating greases or waxes, or coloured or pigmented plastics, non-impact printing material, colour filters, cosmetics or toners comprising high-molecular-weight organic material and a compound of formula (1 ), in a colour-producing amount.
In a special embodiment of the process according to the invention, toners, paints, inks or co-loured plastics are produced by processing master batches of toners, paints, inks or coloured plastics in roil mills or mixing or grinding apparatus.
A colour-producing amount of the compound of formula (1 ) means in the present invention normally from 0.0001 to 99.99 % by weight, preferably from 0.001 to 50 % by weight and es-pecially from 0.01 t~ 50 % by weight, based on the t~tal weight of tile material c~loured or pigmented therewith.
The colouredlpigmented high-molecular-weight materials obtained, such as, for example, plastics, fibres, paints and prints, are distinguished by very high colour intensity, high satura-tion, good fastness to overspraying, good migration-stability, good fastness to heat, light and weathering and by a high gloss and good IR reflectance behaviour.
In order to improve the light fastness properties, UV absorbers are advantageously mixed into the plastics or polymeric particles to be coloured with the compound of formula (1 ) accor-ding to the invention. The amount of UV absorber can vary within a wide range;
advanta-geously there is used from 0.01 to 1.0 % by weight, especially from 0.05 to 0.6 % by weight, more especially from 0.1 to 0.4 % by weight, of a UV absorber, based on the weight of the plastics or polymeric particles.
The following Examples serve to illustrate the invention. Unless otherwise indicated, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres.
Example 1: (general procedure for oxidative dimerization) A solution of 5-phenyl-4-carbethoxy-1,3-dihydro-pyrrol-2-one (10.0 g, 0.04 mol) is heated at 130° C., under stirring in dry DMF (dimethyl formamide) (100 ml). Slow stream of oxygen gas is bubbled through the solution and progress of the reaction is monitored by TLC (~3 hours).
After completion of the reaction, it is poured on water (5-times). Bluish suspension is filtered through Buchner funnel to give dark violet colored crude product (11.0 g). The crude product is purified by selective precipitation from hexane-ethyl acetate solvent mixture to give (2.0 g, 20%) of the pure product. ~H NMR (dmso): ~ 1.1 (6H, t), 4.1 (4H, q), 7.4-7.7 (10H, m), 11.2 (2H, s). All other compounds given in the Table 1 (entries 1, 3, 4, 7) are obtained following the same procedure.
Exa J~le 2: (general procedure for N-butylation) Dimer obtained from process of Example1 (4..5 g, 0.009 mol) is taken in dry DMF (70 ml) under nitrogen atmosphere and the solution is cooled to 5° C. To this sodium hydride 50%
(0.94 g, 0.019 mol) is added in portions. After some time n-butyl bromide (4.65 g, 0.034 mol) is added in cane lot. Reacti~n was monitored by TLC and after the completion, it is poured on brine. Aqueous part is extracted with ethyl acetate, dried over anhydrous sodium sulfate.
Evaporation of organic layer gives the crude violet colored product. It is purified on silica gel column using hexane-ethyl acetate solvent mixture (10 : 90) to give (3.3 g, 58%) of the pure product.'H NMR (dmso): g 0.6(6H, t), 0.8(10H, m), 1.2(4H, t), 3.4(4H, t), 3.9(4H, q), 7.7 (10H, s). All other compounds given in the Table 1 (entries 2, 5, 6) are obtained following the same procedure.
In the following Tables Et means -CH~CHs, Me means -CH3, OMe means -OCH3, t-But means -C(CH3)3, Ph means -Phenyl, OEt means -OCH2CHs and n-But means -(CHZ)3CH3.
Table 1 O
/ Et0 C X
R~ I ZI
\ C / C~ /
X COZEt \ R1 O
Example X R~ Shade (PET) 1 N-H H Violet 2 N-nC4H9 H Violet 3 N-H 4-Me Blue 4 N-H 4-OMe Blue 5 N-nC4H9 4-Me Violet 6 N-nC4H9 4-OMe Violet 7 N-H 4-CI Blue Example 8:
Benzoylacrylic acid (10.Og, 0.056 mol), cuprous chloride (2.0 g, 0.010 mol), ammonium chlo-ride (2,2 g, 0.041 mol) are taken in acetic anhydride (50 ml). It is gradually heated to refilux under stirring for 2 hours. After the reaction is over, it is thoroughly cooled in an ice bath.
Settled solids are filtered through Buchner funnel. Solids are washed with acetic anhydride, water and ethanol to give the crude product (5.2 g). The crude solids are purifiied by soxhlet extraction in toluene to give pure red colored s~lids (3.8 g, 42%). m.
p.315°C, Anal. Calc. For C2oH~aOa; C. 75.94; H, 3.82; Found: C, 74.79; H, 3.82. All other compounds given in the Table 2 are obtained following the above same procedure.
Table 2 O
/ O
R~
i H /
CH /
O R~
O
Example R1 Shade (PET) 8 H Scarlet (fluorescent) 9 4-Me Red 4-t-But Red 11 4-Ph Red 12 4-OMe Red 13 4-O Et Red 14 4-CI Red 4-Br Red 16 3-NO2 Red Example 17:
2.0 g of the above dimmer from Example 8 is taken in acetic acid (50 ml).
Ammonia gas is then bubbled through the solution under reflux for 2 hours. Reaction mixture is cooled to 70° C. and filtered. Solids are washed with water, ethanol and ether.
The crude product is purified by continuous soxhlet extraction to give (1.4 g, 70%) of violet colored product. Anal.
Calc. For CzoH~aN~02; C, 76.42; H, 4.49; N, 8.90; Found: C, 75.84; H, 5.10 ;
N, 7.70. All other compounds given in the Table 3 are obtained following the above same procedure.
Table 3 ~ H
N, R~
CH / CHr /
H \ R~
H
Example R~ Shade (PET) 17 H Violet 18 4-Me Violet 19 4-t-But Violet 4-Ph Violet 21 4-OMe Grey 22 4-OEt Grey 23 4-CI Red 24 4-Br Red 3-NO2 Red Example 26:
2,3-Bis-benzoylamino-succinic acid (5.0 g, 0.014 mol) (synthesized as given in Stachel, S. D.
et al. Arch. Pharm. 312, 968, 1979) is taken in thionyl chloride (50 ml) and refluxed for 2 hours. Excess thionyl chloride is distilled off. Traces of thionyl chloride are removed by tolue-ne co-distillation. It is cooled to room temperature and water is added to it.
The crude mass is then filtered and dried in an oven till constant weight. The red colored pure product obtained, weighted (3.5g, 78%). Anal. Calc. For C~$H~oN~04; C, 67.90; H, 3.17; N, 8.8;
Found: C, 67.07; H, 4.95 ; N, 8.81. All other compounds given in the Table 4 are obtained following the above same procedure.
Table 4 R~
\ N / Ni /
R~
Example R~ Shade (PET) 2G H Red 27 4-Me Red 28 4-CI Red 29 4~-N~2 Red Example 30:
Benzamidine free base (6.0 g, 0.049 mol) and dimethyl acetylenedicarboxylate (3.6 g, 0.025 mol) are taken in benzene (ca. 50 ml). The deep red colored solution obtained is heated to reflux for 2 hours. The cooled mixture is filtered to give (9.0 g) of the crude. The crude pro-duct is taken in minimum amount of warm DMF and poured on large excess of water under stirring. The solids separated (2.1 g) are filtered and soxhlet extracted with methanol for 16 hours. The methanol insoluble pure red colored product obtained, weighted (0.8 g, 10%).
Anal. Calc. For C~gH~2N4O2; C, 68.37; H, 3.79; N, 17.72; Found: C, 69.33; H, 3.43 ; N, 17.47.
Methoxy derivative from Example 31 (see Table 5) is synthesized using above same method.
Table 5 O H
/ N.
\ N / N~ /
N \ R~
H~ O
Example R, Shade (PET) 30 H Yellow 31 4-OMe Orange Example 33:
5-Phenyl-4-carbethoxy-1,3-dihydro-pyrrol-2-one (2.3 g, 0.01 mol) is dissolved in acetic acid (50 ml) at 60 to 70° C. To this PTSA (0.7 g) is added, followed by addition of 2,5-dimethoxy-terephthalaldehyde (1.0 g, 0.005 mol) and temperature is increased to 100° C. Heating is continued for 3 hours and after cooling, solids are filtered through Buchner funnel. The crude product is washed with acetic said, water, DMF and methanol. Finally the crude product is dissolved in cone. sulphuric acid, reprecipitated from water and filtered. It is then dried in an oven to give red colored pure product (1.5 g, 50%). Anal. Calc. For C36H3~N2Oa, C, 69.60; H, 5.15; N, 4.52; Found: G, 66.47; H, 4.98 ; N, 4.34. All other compounds given in the Table 6 are obtained following the above same procedure Table G
/ CO2Et RZ
C O H
/ \ N.
N
O ~n ' C \
I I R~
Rz COZEt /
Example n R~ Rz Shade (PET) 32 0 H H Red 33 1 H OMe Orange 34 1 H H Orange 35 2 H H Yellow 36 0 4-Me H Red 37 1 4-Me H Orange 38 2 4-Me H Yellow 39 0 4-CI H Red 40 1 4-CI H Orange 41 2 4-CI H Yellow 42 0 4-OMe H Red 43 1 4-OMe H Orange Example 44:
5-(p-Methylphenyl)-4-carbethoxy-1,3-dihydro-pyrrol-2-one (5.1 g, 0.0086 mol) is taken in dry DMF (70 ml) under nitrogen atmosphere and the solution is cooled to 5°
C. To this sodium hydride 50% (1.0 g, 0.04 mol) is added in portions. After some time n-butyl bromide (6.35 g, 0.046 mol) is added to it at ones. Reaction is monitored by TLC and after the completion, it is poured on brine. Aqueous part is extracted with ethylacetate, dried over anhydrous sodium sulfate. Evaporation of organic layer gives the crude violet colored product.
It is purified on si-lica gel column using hexane-ethyl acetate solvent mixture (10 : 90) to give (3.5 g,58%) of the pure product.'H NMR (dmso): 5 0.6(6H, t), 0.8(6H, t), 1.2(4H, m), 1.4(4H, m), 2.4(6H, s),3.4(4H, t), 4.0(4H, q), 7.2-8.3(14H, m). All other compounds given in the Table 7 are obtai-ned following the same procedure.
Table 7 R / COZEt R' O ,nBut i / ~ N
N L I / /
nBut~ ~ .
RZ CO2Et / R~
Example n R, R~ Shade (PET) 44 1 4-Me H Gold Yellow 45 1 H H Orange 46 2 H H Yellow 47 0 4-Me H Red 48 0 H H Red 49 2 4-Me H Yellow 50 0 4-CI H Red 51 1 4-CI H Orange 52 2 4-CI H Yellow 53 1 4-OMe H Red Example 54:
Terephthalaldehyde (2.0 g, 0.015 mol), sodium acetate (7.5 g, 0.091 mol) and acetic anhydri-de (70 ml) are taken in round bottom flask and heated to 90° C under nitrogen atmosphere.
To this is added (3-Benzoylpropionic acid (16.0 g, 0.09 mol). Temperature of the reaction is maintained for 3 hours and after cooling solids are filtered through Buchner funnel, washed with acetic acid, water and methanol. The crude product is heated in DMF at 80-90° C for 2 hours. After filtration and washing with water, it is dried in an oven till constant weight to give (5.2g, 83%) of the pure product. Anal. Calc. For Cz$H,$O4; C, 78.37; H, 4.34;
Found: C, 78.87; H, 4.45. The compounds of Examples 55 and 56 (see table 8) are synthesized using above same method.
Table 8 / R
R z O
~ \ iCH / \ O
O L ~ / /
~ ~ 'CH
R~
Rz /
Example n R~ Rz Shade (PET) 54 1 H H Orange 55 1 H OMe Orange 56 2 H H Yellow Example 57:
Above prepared lactone of Example 54 (11.5 g, 0.027 mol) is taken in acetic acid (200 ml).
Ammonia gas is bubbled through it and the solution is refluxed for 2 hours.
After completion of the reaction, it is cooled and filtered. The solids are washed with acetic acid, water and methanol. Final purification is done by stirring the solids in DMF at room temperature for 4-5 hours. Filtered solids are then washed with water, methanol and dried in an oven till constant weight to give (10.2 g, 89%) of the orange colored pure product. Anal. Calc.
For C~$HzoNz02;
C, 80.76; H, 4.80;N, 6.73 Found: C, 80.37; H, 4.14; N, 7.21. Example 58 (see Table 9) is synthesized using above same method.
Example 59:
Above lactam from Example 57 (6.5 g, 0.020 mol) is taken in dry DMF (90 ml) under nitrogen atmosphere and the solution is cooled to 5° C. To this sodium hydride 50% (1.8 g, 0.075 mol) is added in portions. After some time n-butyl bromide (9.90 g, 0.075 mol) is added to it at ones. Reaction is monitored by TLC and after completion, it is poured on brine. Aqueous part is extracted with ethyl acetate, dried over anhydrous sodium sulfate.
Evaporation of or-ganic layer gives the crude orange colored product. It is purified on silica gel column using hexane-ethyl acetate solvent mixture (10 : 90) to give orange colored (2.0 g,18%) of the pure product. m. p. 160°C; ~H NMR (cdcls): ~ 0.8(6H, t), 1.2(4H, t), 1.4(4H, m), 3.7(4H, t), 6.2(2H, s), 7.2-7.6(16H, m).
Table 9 / R
R
\ X
X / / ~ \
~ ~ CH
R~
R~ /
Example X n R~ Rz Shade (PET) 57 NH 1 H H Orange 58 NH 2 H H Yellow 59 N-nBut1 H H ~range Example 60:
Terephthalaldehyde (7.0 g, 0.055 mol), sodium acetate (14 g, 0.017 mol) and acetic anhydri-de (150 ml) are taken in round bottom flask and heated to 90° C under nitrogen atmosphere.
To this is added hippuric acid (30.0 g, 0.167 mol). Temperature of the reaction is maintained for 4 hours and after cooling yellow solids are filtered through Buchner funnel, washed with acetic acid, water and methanol. The crude product is heated in DMF at 80-90° C for 2 hours. After filtration and washing with water, it is dried in an oven till constant weight to give (14.5g, 66%) of the pure product. Anal. Calc. For C~sH~6Na04; C, 74.28; H, 3.84;N, 6.66 Found: C, 73.57; H, 3.67; N, 6.79.
Table 10 / ~ R
R z O
1 \ ~N / \ O
O ~I / /
O )n ~ N I \
R~
R~ /
Example n R~ R2 Shade (PET) 60 1 H H Yellow (fluorescent) 61 0 H H Orange 62 2 H H Yellow Example 63:
Above oxazoline based compound of Example 61 (1.0 g, 0.0023 mole) is taken in acetic acid (30 ml). The reaction mixture is refluxed while ammonia gas is bubbled through the solution for 2 hours. The reaction mixture is filtered after cooling and washed with acetic acid, water and methanol. The crude mass is stirred in DMF at room temperature for 15 hours followed by boiling in water f~r 3 hours. Final wash is given with methanol and dried in an oven till constant weight. The pure product obfiained in this way gives (2.5 g, 22%) yield of the pure product. Anal. Calc. For G2~H,gN402; C, 74.64; H, 4.34;N, 13.79 Found: C, 72.75; H, 4.19; N, 13.60.
Table 11 / R
R ~ O
iN / \ N -H
H- N ~ I / /
O .~ ' N I \
R~
R~ /
Example n R~ R2 Shade (PET) 63 1 H H Orange 64 2 H H Yellow Dyeing Example 1:
1200.00 g of polyester granules (PET Arnite D04-300, DSM) are pre-dried for 4 hours at 130°C and then mixed homogeneously with 2.6 g of the compound of formula i C i ~ ~ (100) O H
O
in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute.
The homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin, D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 275°C, cooled with water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) and then dried for 4 hours at 130°C.
The resulting greenish yellow-coloured polyester granules have good allround fastness pro-perties, especially good light fastness and high-temperature light fastness properties.
Dyeing Example 2:
1200.00 g of polyamide-6 granules (lJltramid 831, BASF) are pre-dried for 4 hours at 75°C
and then mixed homogeneously with 3.5 g of the compound of formula OC H ~ ~HaOHZCHZGH3 z s C ~ H i /
i ~ \ / H I ~ (108) C=O
1 O Oc2H5 H3CHzCHzCHzC
in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute.
The homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin, D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 220°C, cooled with water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) and then dried for 4 hours at 75°C.
The resulting orange-coloured polyamide granules have good allround fastness properties, especially good light fastness and high-temperature light fastness properties.
Claims (7)
1. Compounds of formula (1) wherein R1 is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfo-nic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, R'1 is hydrogen, hydroxy, halogen, nitro, cyano, amino, carboxy, carboxylic ester, sulfo, sulfonic ester, carboxylic amide, sulfonic amide, alkylthio, arylthio, alkoxy or aryloxy, X is -O-, -S-, -NH- or-N(alkyl)-, X' is -O-, -S-, -NH- or-N(alkyl)-, Y is hydrogen or carboxylic ester, Y' is hydrogen or Carboxylic ester, Z is =C- or =N-, Z' is =C- or =N-, x is 0 or 1, when Z is =N-, then x is 0, y is 0 or 1, when Z' is =N-, then y is 0, A is a conjugated linking bridge of the for-mule wherein n is 0, 1, 2 or 3, m is 0, 1, 2 or 3, B is a phenyl ring, T is =C(R3)- or =N-, wherein R3 is hydro-gen, C1-C12alkyl or CN, W is a heterocyclic, or linear or polycondensed aromatic group which is unsubstituted or substituted by alkyl, halogen, hydroxy, alkoxy, alkylthio or amino, G is -CH= or-N=, and R2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkylthio or amino.
2. Compounds according to claim 1, wherein R1 is hydrogen, chloro, bromo, methyl, metho-xy, ethoxy, tert.-butyl, , phenyl or vitro is, R2 is hydrogen, chloro, bromo, methyl, methoxy, ethoxy, tert.-butyl, , phenyl or vitro, R2 is hydrogen or methoxy, X is -NH-, -N(n-C4H9)-, or -O-, X' is -NH-, -N(n-C4H9)-, or -O-, Y is hydrogen or COOC2H5, Y' is hydrogen or COOC2H5, Z is =C- or =N-, Z' is =C- or =N-, A is = or = = T is =C(r3)-, R3 is hydrogen and n is 0, 1 or 2.
3. Compounds according to either claim 1 or claim 2 of formula
4) Process for the preparation of compounds of formula (1), which process comprises reac-ting 2 mol of compound of formula (50) which possess an active methylene group-CH2 or 1 mol of compound of formula (50) and 1 mol of compound of formula (51), which possess an active methylene group -CH2 with 1 mol of one of the compounds of formula wherein R1, R'1, X, X', Y, Y', Z, Z', x and y are as defined above for formula (1), n is 0, 1, 2 or 3, m is 0, 1, 2 or 3, B is a phenyl ring, R2 is hydrogen, alkyl, halogen, hydroxy, alkoxy, alkyl-thio or amino and R3 is hydrogen, C1-C12alkyl or CN, at elevated temperature or by oxidation 2 mol of compound of formula (50) at elevated temperature or by oxidation 1 mol of compound of formula (50) and 1 mol of compound of formula (51) at elevated temperature.
5) Process for the preparation of coloured or pigmented plastics or polymeric coloured particles, which process comprises mixing together a high-molecular-weight organic material and a colour-producing amount of at least one compound of formula (1) according to claim 1.
6) Coloured or pigmented plastics or polymeric coloured particles comprising compound of formula (1) according to claim 1.
7) Use of the compounds of formula (1) according to claim 1 for the production of inks, for printing inks in printing processes, for flexographic printing, screen printing, the printing of packaging, security colour printing, intaglio printing or offset printing, for preliminary printing stages and for textile printing, for office and home use or for graphics, such as, for example, for paper goods, for ball-point pens, felt-tip pens, fibre-tip pens, paperboard, wood, (wood) stains, metal, stamp pads or inks for impact printing processes (with impact printing ink rib-bons), for the production of colourants, for paints, for use in industry or advertising, for textile decoration and industrial labelling, for roll coating or powder coating compositions or for automobile paints, for high-solids (low-solvent), water-containing or metallic paints or for pig-mented formulations for aqueous paints, for mineral oils, lubricating greases or waxes, for the production of coloured plastics for coatings, fibres, plates or moulded substrates, for the production of non-impact printing material for digital printing, for the thermal wax-transfer printing process, the ink-jet printing process or for the thermal transfer printing process, and also for the production of colour filters, especially for visible light in the range of from 400 to 700 nm, for liquid crystal displays (LCD) or charge-coupled devices (CCDs) or for the pro-duction of cosmetics or for the production of polymeric colour particles, toners, dry copy to-ners, liquid copy toners or electrophotographic toners, or for optical information storage appli-cations (ois).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN228CH2003 | 2003-03-19 | ||
| IN228/MAS/2003 | 2003-03-19 | ||
| PCT/EP2004/050276 WO2004089941A1 (en) | 2003-03-19 | 2004-03-10 | New heterocyclic compounds, a process for their preparation and their use as dyes and pigments |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2519157A1 true CA2519157A1 (en) | 2004-10-21 |
Family
ID=33156196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002519157A Abandoned CA2519157A1 (en) | 2003-03-19 | 2004-03-10 | New heterocyclic compounds, a process for their preparation and their use as dyes and pigments |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1603902A1 (en) |
| CA (1) | CA2519157A1 (en) |
| WO (1) | WO2004089941A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008106021A (en) * | 2006-10-27 | 2008-05-08 | Dainippon Ink & Chem Inc | Method for producing pyrrolinone compound, and method for producing bipyrrolinone compound |
| CN103664916B (en) * | 2012-09-12 | 2016-08-24 | 中国科学院化学研究所 | Conjugation small molecule material based on sub-two pyrroles of bithiophene and derivant thereof and preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2440405A1 (en) * | 1974-08-23 | 1976-03-04 | Basf Ag | Modifcn. of azlactone dispersion dye - into stable form by heat treatment |
| DE2608481C2 (en) * | 1976-03-02 | 1978-03-30 | Hoechst Ag, 6000 Frankfurt | Process for coloring water-insoluble, thermoplastic polymers and polycondensates in bulk |
-
2004
- 2004-03-10 WO PCT/EP2004/050276 patent/WO2004089941A1/en active Application Filing
- 2004-03-10 EP EP04741425A patent/EP1603902A1/en not_active Withdrawn
- 2004-03-10 CA CA002519157A patent/CA2519157A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004089941A1 (en) | 2004-10-21 |
| EP1603902A1 (en) | 2005-12-14 |
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