Title of Invention	A PROCESS FOR PREPARING AN ALKYLTHIO-AND/OR ARYLTHIO- SUBSTITUTED DIKETO-DIARYL-PYRROLOPYRROLE(DPP)
Abstract	This invention relates to a preparation of alkylthio and/or arylthio-substituted diketo- diaryl-pyrrolopyrroles (DPPs) of the formula la and dithio-bridged bis-diketo-diaryl- pyrrolopyrroles (bis-DPPs) of the formula Ib which comprises reacting a thiol or thiolate with a halo-diketo-diaryl-pyrrolopyrrole ("halo- DPP") of the formula IIa or reacting a dithiol or dithiolate with two halo-diketo-diaryl-pyrrolopyrroles ("halo-DPPs") of the formula lIb Hal H 2b, Gs in which G, G1, G2, G3, Gs, G6, G7, and Hal have the meaning as described in claim 1, and also novel DPPs and also bis-DPPs, compositions comprising the DPPs of the formula la prepared according to the invention, and their uses.

Title of Invention

A PROCESS FOR PREPARING AN ALKYLTHIO-AND/OR ARYLTHIO- SUBSTITUTED DIKETO-DIARYL-PYRROLOPYRROLE(DPP)

Abstract

This invention relates to a preparation of alkylthio and/or arylthio-substituted diketo- diaryl-pyrrolopyrroles (DPPs) of the formula la and dithio-bridged bis-diketo-diaryl- pyrrolopyrroles (bis-DPPs) of the formula Ib which comprises reacting a thiol or thiolate with a halo-diketo-diaryl-pyrrolopyrrole ("halo- DPP") of the formula IIa or reacting a dithiol or dithiolate with two halo-diketo-diaryl-pyrrolopyrroles ("halo-DPPs") of the formula lIb Hal H 2b, Gs in which G, G1, G2, G3, Gs, G6, G7, and Hal have the meaning as described in claim 1, and also novel DPPs and also bis-DPPs, compositions comprising the DPPs of the formula la prepared according to the invention, and their uses.

Full Text	The present invention relates to an improved process for preparing atkyltliio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrroles (DPPs) of the formula la and dithio-bridged bis-diketo-diaryl-pyrrolopyrroles (bis-DPPs) of the formula lb in which in formula la G is phenyl substituted by at least one arylthio or aikylthio group, and G1is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate, and in formula lb Gs is a phenylene, Ge is G1 but not G, and G7 is alkylene or phenylene, by reacting two haloaryls with a dithiol or dithiolate. The invention additionally relates to novel, arylthio- or alkylthio-substituted DPPs, their use, and compositions comprising the DPPs of the invention. US 4,579,949 and US 4,490,542 describe the preparation of DPPs substituted by at least one thioether group by reacting arylthio- or alkylthio-substituted benzonitriles with succinic esters. Disadvantages are the low yields in the case of long-chain alkylthio-DPPs and the impossibility of obtaining water-soluble compounds. The reaction of DPP pigments with thiols to give aikylthio- or arylthio-substituted DPPs gives incomplete conversions owing to the poor solubility of these pigments. Chemistry Letters 1978.13-14 discloses that unactivated haloaryls can be substituted only in the presence of catalysts. It was therefore an object of the invention to provide an improved process for preparing alkylthio- and/or arylthio-substituted DPPs which permits in particular the preparation of water-soluble compounds and long-chain alkylthio-DPPs. In particular, the process should be operable without high pressures and the use of catalysts. In addition, the economics of the process should be guaranteed by high yields. Furthermore, the invention was to provide novel, thioether-substituted diketo-diaryl-pyrrolopyrroles and also dithioether-bridged bis-DPPs which can be used in compositions with high molecular mass organic material, in particular as colorants. In addition, the thioether-substituted DPPs should be able to be used, in particular, as crystal growth inhibitors or rheology enhancers. Accordingly, we have found the process defined at the outset, which involves reacting a thiol or thiolate with a halo-diketo-diaryl-pyrrolopyrrole ("halo-DPP") of the formula lla " 0 ■* in which Hal is halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine and. with particular preference, chlorine, Hal being, in particular, in the para position of the phenylene. Customarily, the reaction is started by bringing the thiol and/or thiolate or the dithiol and/or the dithiolate into contact with the halo-DPP lla or lib by conventional methods, for example by mixing the starting materials or by dropwise addition of one starting material to the other. To prepare the compounds of the formula la the molar ratio of thiol to halo-DPP of the formula lla is generally chosen to be within the range from 0.1:1 to 20:1. preferably in the range from 2:1 to 5:1 and, with particular preference, in the range from 2.1:1 to 2.7:1, and, to prepare the compounds of the formula lb, the molar ratio of dithiol to halo-DPP of the formula lib is generally chosen to be in the range from 0.5:1 to 20:1, preferably in the range from 0.5:1 to 5:1 and. with particular preference, in the range from 1:1 to 2.7:1. Preferably, the reaction temperature is chosen to be within the range from 323 to 453 K, preferably in the range from 333 to 433 K, with particular preference in the range from 343 to 423 K and, with very particular preference, in the range from 343 to 413 K. The reaction pressure is chosen to be generally within the range from 70 kPa to 10 f^Pa, preferably from 90 kPa to 5 MPa; atmospheric pressure is particularly preferred. The reaction time depends generally on the reactivity of the starting materials, the chosen reaction temperature and the desired conversion. The reaction time is customarily chosen to be within the range from 15 minutes to 2 days. In one preferred embodiment the reaction is conducted under an inert gas atmosphere using for this purpose preferably nitrogen or noble gases such as helium or argon. Particular preference is given to reaction in a nitrogen atmosphere. In addition, the reaction can be carried out with or without solvent, with preference being given to reaction in a solvent. Preferred solvents are organic solvents or solvent mixtures such as aprotic, especially non-aqueous aprotic, solvents. Aprotic solvents may be apolar, such as benzene, chlorobenzene and chlorinated hydrocarbons, or polar. The latter are particularly preferred. Examples of polar aprotic solvents which can be used are amides such as hexamethyl-phosphoramide. carboxamides such as N,N'-dimethylformamide and N.N'-dimethylacetamide, or lactams such as N-methylpyrrolidone, N-methyl-2-piperidone, 1,3-dimethyl-3.4,5,6-tetrahydro-3(1H)pyrimidinone or N-methyl-4-piperidone, or urea bases such as N,N' -dimethylethyleneurea, N,N'-dimethyl-propyleneurea. and also acetonitrile, sulfolane, dimethyl sulfoxide, or aromatic solvents such as nitrobenzene. Preference is given to N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-3,4,5,6-tetrahydro-3(1H)pyrimidinone or N-methyl-pyrrolidone. The weight ratio of halo-DPP lla or halo-DPP lib to the solvent lies in general within the range from 0.5 to 10% by weight, with particular preference in the range from 1 to 5% by weight and, with very particular preference, in the range from 2 to 3% by weight. In another preferred embodiment the reaction is conducted in the presence of a base. Examples of suitable bases are alkali metal carbonates, for example Na2CO3 or K2CO3, alkali metal hydrogencarbonates, for example NaHCOa or KHCO3, alkali metal hydroxides, for example NaOH or KOH. alkali metals, such as sodium or potassium, and also aromatic bases, such as pyridine, N,N'-dimethylaminopyridine or quinoline. Preference is given to non-aqueous alkali metal bases and to aromatic bases, particular preference to non-aqueous alkali metal carbonates or alkali metal hydrogencarbonates, and very particular preference to anhydrous K2CO3. The molar ratio of base to thiol or thiolate lies customarily within the range from 0.5:1 to 5:1, preferably in the range from 1:1 to 4:1 and, with particular preference, in the range from 1:1 to 3:1, and the molar ratio of base to dithiol or dithiolate lies customarily within the range from 1:1 to 10:1, preferably within the range from 1:1 to 5:1 and. with particular preference, in the range from 1:1 to 4:1. In a preferred embodiment of the process of the invention the reaction is ■4 conducted in the presence of a solvent or solvent mixture and a base. If desired, the reaction can also be conducted in the presence of catalysts, especially transition metal catalysts, examples being tetrakis(triphenyl-phosphine)palladium(O), -nickel(O), and -platinum(O), and -ruthenium(ll) chloride. Preferably, the reaction is conducted without a catalyst. If a catalyst is used, it is generally employed in a proportion within the range from 0.001 to 10% by weight, based on halo-DPP of the formula lla or lib, and preferably from 0.5 to 7% by weight and. with particular preference, from 2 to 5% by weight based on the total amount of reactants. The reaction mixture can be worked up by conventional methods, for example by filtration and subsequent washing of the filter residue and subsequent optional drying. The product may be an individual compound or a mixture of differently substituted compounds of the formula la, or a mixture consisting of halo-DPP lla and a compound of the formula la, or else a mixture consisting of halo-DPP lib and a compound of the formula lb and/or la. In accordance with observations made to date the thiol or thiolate employed can comprise any known thiols or thiolates, examples being substituted or unsubstituted aryl or alkyl thiolates, it being possible for the latter to be branched or straight-chain, uninterrupted, or interrupted one or more times by heteroatoms. In a preferred embodiment a thiol or thiolate of the formula ilia or a dithiol or dithiolate of the formula lllb is used. in which Ri can be C1-C30alkyi which can be uninterrupted or intermpted one or more times by heteroatoms, such as -0- or -S-, or by -NH-, -C(0)0-, -Q-C(O)- or -C(0)-NH-, and can be substituted or unsubstituted, or can be C5-Ci2cycloalkyl or phenyl, each of which can be substituted or unsubstituted, and R2 is hydrogen, a cation ("M") of an alkali metal, or an organic nitrogen base, and G7 can be C1-C30alkylene which can be uninterrupted or interrupted one or more times by heteroatoms. such as -0- or -S-. or by -NH-. -C(0)0-. -O-C(O)- or -C(0)- NH-. and can be substituted or unsubstituted, or can be C5-C12cycloalkylene or phenylene, each of which can be substituted or unsubstituted. C1-C30aikyl is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl. tert-amyl, hexyl, 2.2-dimethylbutyi, heptyl, octyl, 2-ethylhexyl, 1,1',3,3'- tetramethyibutyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl. octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl or nonacosyl, preference being given to C1-C18alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl, tert-amyl, hexyl, 2,2-dimethylbutyl, heptyl, octyl, 2-ethylhexyl, 1,1\3,3'-tetramethylbutyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl and particular preference to C8-C18alkyI such as octyl, 2-ethylhexyl, 1,V,3,3'-tetramethylbutyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl and very particular preference to C12-C18alkyl such as dodecyl. tridecyl, tetradecyl, pentadecyl. hexadecyl, heptadecyl or octadecyl; particular preference is also given to C1-C8alkyI such as methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl, tert-amyl. hexyl. 2,2'-dimethyIbutyl, heptyl. octyl, 2-ethylhexyl and 1,1',3,3'-tetramethylbutyL C1-C30alkylene is methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene. sec-amylene, tert-amylene, hexylene, 2,2'-dimethylbutylene, heptylene, octylene, 2-ethylhexylene, 1,1',3,3'-tetramethylbutylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, eicosylene, heneicosylene, docosylene, tetracosylene. pentacosylene, hexacosylene. heptacosylene, octacosylene or nonacosylene, preference being given to C1-C18alkylene such as methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, sec-amylene, tert-amylene, hexylene, 2,2'-dimethylbutylene, heptylene. octylene, 2-ethylhexylene, 1,1'.3,3'-tetramethylbutylene, nonylene, decylene, dodecylene. tetradecylene, hexadecylene or octadecylene, and particular preference to C8-C18alkylene such as octylene, 2-ethylhexylene, 1.1'.3,3'-tetramethylbutylene, nonylene. decylene, dodecylene, tetradecylene, hexadecylene or octadecylene; in addition, particular preference is given to C1-C8alkylene such as methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, sec-amylene, tert-amylene, hexylene, 2,2'-dimethylbutylene, heptylene. octylene, 2-ethyl-hexylene or 1,1',3,3'-tetramethylbutylene. C8-C18cycloalkyI is for example cyclopentyl, cyclohexyl, cycioheptyl or cyclooctyl, preferably C5-C6cycloalkyi such as cyclopentyl or cyclohexyl. C5-C12cycloalkylene is for example cyciopentylene, cyclohexylene, cycloheptylene or cyclooctylene, preferably C5-C6cycloalkylene such as cyciopentylene or cyclohexylene. Alkyl radicals or aikylene radicals of at least two carbon atoms, represented by Ri or Gy, can be interrupted one or more times by for example -0-, -NH-, -C(0)0-, -O-C(O)-, -C(0)-NH-; preference is given to -C(0)0- or -0- and very particular preference to the -C(0)0-internjpted alkyl radical -CH2-C(0)0-CH2CH3, or the singly -0-interrupted alkyl radical such as -CH2-CH2-O-CH2-CH3, or the doubly -0-interrupted alkyl radical such as -CH2-CH2-O- Cn2—CH2—O—CH2—CH3. In addition, the alkyl or cycloalkyi radicals or the phenyl radical of R1 can be substituted by, for example, the following radicals: C1-C18alkyl, OR3. S-R3. C(0)R3. COOR3, -OCOR3. SO3R3, SO2R3. PO3R3. Si(0R)3, a salt radical such as S-M, 0-M, COOM, SO3M, POafvl, P(R3)3' X', P((R3)2 R4 )3' X", NO2, N(R3)3' X", N((R3)2 R4 )3' X' or a nitrogen-containing radical, in which R3 and R4 independently of one another are hydrogen. C1-C18alkyI, especially methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl, tert-amyl. hexyl or 2,2-dimethylbutyl, or are C5-C6cycloalkyI or unsUbstituted or Ry-substituted phenyl, M is a cation of an alkali metal, preferably sodium or potassium. X" is a halide, such "as fluoride, chloride, bromide or iodide, and R7 is hydrogen, halogen such as F, CI, Br, I or is C1-C8alkyl or unsubstituted or NR3R4- substituted C5-C6cycloalkyl. Preferred OR3 is OH. and preferred S-R3 is SH. Preferred radicals COOR3 are COOH. COOCH3, COOC2H5, COOC4H9, COOC5H11. and preferred -OCOR3 is -0-CO-C(CH2)-CH3. Preferred radicals SO3R3 are SO3H, S03(C5H4)R7. SOaCCsHg), SO3CH3, SO3C2H5. and preferred radicals SO2R3 are S02(C5H4)R7. S02(C5H4) or SO2CH3. Preferred radicals PO3R3 are PO3H, P03(C5H4)R7 or PO3CH3, Preferred nitrogen-containing radicals are selected from the group consisting of NR3R4. especially NH2. NHR3 or N(R3 R4), with particular preference being given to substituted alky! radicals, such as (R3 R4)N-{C1-C3oalkyl)-, especially (CH3)2N-C2H5-, further preferred nitrogen-containing radicals are selected from the group consisting of CONHNH2, CONHR3, NHCOR3. NCO and a heterocyclic radical and a compound selected from the group of the formulae IV to IX selected in particular from the group of the compounds of the formulae IV and V, in which t' R5 independently of R? has the same definition as R7. and Re is a direct bond, -CH2-. -CH(CH3)-, -C(CH3)2-, -CH=N-. -N=N-, -0-, -S-, -SO-. -SO2- or -NR3-. and r is zero or an integer from 1 to 17. Furthermore, the alkyiene, cycloaikylene or phenylene radical of G7 can be substituted by, for example, the following radicals: halogens such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine and. with particular preference, chlorine; -E-C1C18alkyI, in which E is -0-, -S-, -NH-, -C(0)0-, -00(0)-. -NHC(O)-, -C(0)NH-; CN, NO2, CFa or c1-C18alkyl, which can be uninterrupted or interrupted one or more times by heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(O)- or -C(0)-NH-. If E is -0-. then -O-Ci-CisalkyI can be methoxy, ethoxy, n-propoxy, isopropoxy, hexadecyloxy or octadecyloxy, preferably methoxy or ethoxy and, with very particular preference, methoxy. If E is -S-, then -S-C1-C18alkyl can be methylmercapto, ethylmercapto, n-propylmercapto, isopropylmercapto, hexadecylmercapto or ocatdecylmercapto, preferably methylmercapto or ethylmercapto and, with very particular preference, methylmercapto. If E is -NH-, then -NH-C1-C18aikyi can be methylamine, ethylamine, n-propylamine, isopropylamine, hexadecylamine or octadecylamine, preferably methylamine or ethylamine and, with very particular preference, methylamine. If E is -C(0)0- then -C(0)0-C1-C18alkyI can be methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, hexadecoxycarbonyl or octadecoxycarbonyi, preferably methoxycarbonyl or ethoxycarbonyl and, with very particular preference, methoxycarbonyl. If E is -0C(0)- then -0C(0)-C1-C18alkyl can be a methyl, ethyl, n-propyl, isopropyl, hexadecyl or octadecyl ester radical, preferably a methyl or ethyl ester radical and, with very particular preference, a methyl ester radical. If E is -C(0)NH- then -C(0)NH-C1-C18alkyl can be a methyl-, ethyl-, n-propyl-. isopropyl-, hexadecyl- or octadecylaminocarbonyl radical, preferably a methyl- or ethylaminocarbonyl radical and, with very particular preference, methyl-aminocarbo'nyl radical. If E is -NHC(O)- then -NHC(0)-C1-C18alkyl can be a methyl-, ethyl-, n-propyl-, isopropyl-, hexadecyl- or octadecylcarbonylamino radical, preferably a methyl- or ethylcarbonylamino radical and, with very particular preference, methylcarbonylamino radical. Preferred substituted alkylene radicals for G7 are symmetrically substituted radicals such as -(CH2)m-CH(C1-C30alkyl)-(CH2)m or -(CH2)m-C(C1-C30alkyl)2-(CH2)m. in which m is an integer in the range from 1 to 14, with particular preference an integer in the range from 3 to 8. Preferred substituted phenylene radical G7 possesses one or two substituents such as halogen, C1-C18alkyi, -O-C1-C18alkyI, -S-C1-C18alkyI, -NH-C1-C18alkyI, CN, NO2 or CF3, where the substituents can be identical or different. Heterocyclic radical is, for example, a five-membered nitrogen-containing heterocyclic radical such as imidazolyl, pyrazolyl, triazolyl, pyrrolyl, pyrrolidinyl, oxazolyl or thiazolyl, a six-membered nitrogen-containing heterocyclic radical such as piperazinyl, piperidinyl, pyridinyl or morpholinyl, or a bicyclic radical which possesses a fused-on five-membered nitrogen-containing heterocycle and a six-membered aromatic ring, such as benzoxazolyl, indolyl, benzothiazolyl, benzimidazolyl or benzotriazolyl. Examples of suitable organic nitrogen bases for R2 are pyridine, morpholine, N,N'-dimethylaminopyridine and quinoline. Particular preference is given to thiols such as C1-C18alkyl-SH, especially H-S-(CH2)n-CH3, in which n is an integer from 8 to 17, H-S-CH2COOC2H5. H-S-CH2CH2COOC2H5, H-S-(para-methylphenyl), H-S-(para-hydroxyphenyl), and also H-S-(CH2)nrNR3R4 in which n1 is an integer from 8 to 18, H-S-{CH2)2N(CH3)2, and also thiolates such as sodium salts or potassium salts of 'S-id-Ciealkyl), 'S-(CH2)2-OH. •S-CH2COOC2H5. "S-Cpara-methylphenyl), ■S-(para-hydroxyphenyl) or ■S-(CH2)2N(CH3)2. Particularly preferred dithiols are -S-(C1-C18alkylene)-S-. especially -S-(C3-C8alkylene)-S-, such as -S-(CH2)3-S-, -S-(CH2)4-S-, -S-(CH2)5-S-, -S-(CH2)6-S-, -S-(CH2)7-S- or -S-(CH2)8-S-. and very particularly preferred dithiols are -S-(CH2)3-S-. -S-(CH2)5-S- or -S-(CH2)6-S-. The thiols, dithiols or thiolates, dithiolates of the formula I11a or 111b are obtainable commercially or by known methods for preparing thiols, dithiols or thjolates. dithiolates (Houben-Weyl, Methoden der organischen Chemie, Volume E 11, pp. 32-63, Georg Thieme Verlag, Stuttgart, New York, 1985; and J.L. Wardell, "Preparation of Thiols", in S. PATAI (ed.), The chemistry of the thiol group, pp. 163-269. John Wiley & Sons, London. New York, 1974). In the process of the invention a halo-DPP of the formula Ha is used in which G2 is a halogenated phenyl group and G3 is G2 or G1i, and G3 is preferably G2 or a carbocyclic or heterocyclic radical and with particular preference is G2; in other words, the halo-DPP of the formula lla in that case is a symmetrically substituted halo-DPP. If G3 or Ge is G1, then the radical involved can also be a heterocyclic radical which corresponds to the above definition of heterocyclic radicals and is additionally pyrimidine, thiophene or furan, or else the radical involved can be a carbocyclic group of the formula XI, XllorXlil in which R8. R9. Rio and R11 independently of one another are hydrogen, halogen such as fluorine, chlorine, bromine or iodine or C1-C18alkyI, and in particular hydrogen,C1-C5alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl. sec-butyl, tert-butyl, n-pentyl, sec-amyl or tert-amyl. or halogen such as CI or Br, and R12 is a single bond, -CH2-. -CHCCH3)-, -C(CH3)2-. -CH=N-, -N=N-. -0-, -S-, -SO-, -SO2- or -NR3-. With particular preference, halo-DPP of the formula lib together with G6 is an organic radical such as in which R40 and R41 independently of one another are hydrogen, halogen such as fluorine, chlorine, bromine or iodine, or C1-C18alkyI, -E-C1-C18alkyi. -CN. -NO2 or trifluoromethyl. With very particular preference G6 is an organic radical such as in which R42 and R43 independently of one another are hydrogen, chlorine, methyl, tert-butyl or -CN. In one preferred embodiment the halogenated phenyl group G2 employed is a compound of the formula XIV in which Hal is halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine. With particular preference, halogen is in the para position. If desired, the halogenated phenyl group G2 can be a compound of the formula XV and can carry further substituents, R13 or R14, where R13and R14 independently of one another are, for example, hydrogen, CN, CF3, C1-C5aikyl, C5-C6cycloalkyi, -E-C1-C18alkyI, phenyl, S-Ri, amides such as -CONR3R4 or amides of the formulae XVI to XIX or amides of nitrogen-containing heterocycles such as 1-carbonyl-imidazole, -pyrazoie. -triazole, -pyrrole, -pyrrolidine, -benzimidazole or -benzotriazole, or halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine. Preferably, R13 and R14 are in the meta positions. In a further preference, R14 is hydrogen and R13 is one of the above substituents other than hydrogen, preferably in the meta position. In another preferred embodiment the halogenated phenyl group G2 is of the formula XX in which Hal is preferably fluorine, chlorine, bromine or iodine and. with particular preference, chlorine or bromine. Halo-DPPs II with correspondingly substituted groups are known, for example, from patents US 5,484,943, US 5,616,725 or US 5,200,528 or are obtainable in accordance with US 4,579,949. A further embodiment of the present invention relates to new DPPs of the formulae XXI and XXX in which R15. R16. R20 and R21 independently of one another are hydrogen or R1aor Ru, and G4 is a carbocyclic or heterocyclic radical, with the proviso that (a) R1 in formula XXI is not phenyl if R15 and R16 are hydrogen and G4 is phenyl, and (b) R1 in formula XXX is not phenylene(CrC4alkyl) or C1-C12alkyl if R15. R16. R20 and R21 are hydrogen, and G5 is a phenylene, G6 is a carbocyclic or heterocyclic radical, and G7 is alkylene, cycloalkylene or phenylene. Preferred DPPs of the fonnula XXI or XXX are those in which R1 is mono- or polysubstituted or unsubstituted C1-C30alkyl or a phenyl radical. With particular preference. R15, R1. R20 and R21 are hydrogen and R1 is -C1-C18alkyl. such as C4alkyl, C6alkyI, C9alkyl. C12alkyl or C6alkyl. and also -(para- phenylene)-OH, -CH2CH2OH, -CH2C(0)0-CH2CH3, -(CH2)2C(0)0-CH2CH3 -(C1-C30alkylene)-N(R3,R4) such as -(C2H5)-N(CH3)2. Particular preference is G1ven to compounds of the formula lb in which G5 is 1,4-phenylene and G7 is n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene or n-octyiene, or substituted or unsubstituted phenylene and Geis unsubstituted or substituted phenyl. Very particular preference is G1ven to compounds of the formula lb in which G5 is 1,4-phenylene and G? is n-propylene, n-butylene, n-pentylene, n-hexyiene. n-heptylene or n-octylene and Ge is unsubstituted phenyl. Very particular preference is G1ven to compounds of the formula XXXI or XXXII A further embodiment of the present invention relates to compositions compR1sing a DPP of the formula la and a halo-DPP of the formula lla, obtainable by the process of the invention using a substoichiometR1c amount of thiol or thiolate of the formula Ilia. Preferably, the thiol or thiolate of the formula Ilia is employed in a molar ratio that is within the range from 0.1 to 49%, based on the total amount of thiol or thiolate of the formula Il1a and halo-DPP of the formula lla. A further embodiment of the process of the invention relates to compositions compR1sing at least two differently substituted DPPs of the formula la. These compositions are obtainable either by reacting at least two differently substituted halo-DPPs of the formula lla with a thiol or thiolate of the formula Ilia or, conversely, by reacting at least two differently substituted thiols or thiolates of the formula Ilia with a halo-DPP of the formula lla. The molar ratio of thiol or thiolate of the formula Ilia to differently substituted halo-DPPs of the formula lla, or of differently substituted thiols or thiolates of the formula Ilia to halo-DPP of the formula lla, is generally chosen to be within the range from 20:0.1 to 1:1, preferably in the range from 10:1 to 5:1 and, with very particular preference, within the range from 5:1 to 5:2. The molar ratio of the differently substituted halo-DPPs of the formula lla to one another is generally chosen to be within the range from 0.1 to 99.9 mol-%, based on the total amount of differently substituted halo-DPPs of the formula lla, and is preferably in the range from 20 to 80 mol-% and, with particular preference, in the range from 40 to 60 mol-%. The molar ratio of differently substituted thiols or thiolates of the formula Ilia to one another is generally chosen to be within the range from 0.1 to 99.9 mol-%. based on the total amount of differently substituted thiols or thiolates of the formula Ilia, is preferably within the range from 20 to 80 mol-% and, with particular preference, in the range from 40 to 60 mol-%. The invention relates, furthermore, to compositions compR1sing a DPP of the formula XXI and/or XXX and/or DPP la and/or lb and diketo-jdiaryl-pyrrolopyrrole (DPP) or a DPP latent pigment, wherein DPPs of formula XXI and la, or XXX and lb are different. DPP latent pigments are descR1bed, for example, in US 5,616.725. In a preferred embodiment, the molar ratio of DPP of the formula XXI and/or XXX to DPP. DPP of the formula la or lb. or DPP latent pigment is chosen to be within the range from 0.1 to 99.9 mol-%, based on the total amount of DPP of the formula XXI or XXX, DPP or DPP latent pigment, more preferably from 20 to 80 mol-% and. with particular preference, from 40 to 60 mol-%. These compositions of the invention can be prepared by customary methods, for example, by mixing the individual components with one another in accordance with the customary methods, in analogy, for example, to the method descR1bed in US 5.200.528. The DPPs can be prepared by customary methods as descR1bed in US 5,200,528. Similarly, the DPP latent pigments can be prepared in analogy to the method descR1bed in US 5,561,232. Furthermore, the invention relates to the use of DPP of the formula la and/or lb as rheology enhancers or as crystal growth inhibitors. A further embodiment of the present invention relates to the use of DPPs of the formula XXI or XXX as rheology enhancers or as crystal growth inhibitors. In addition, the invention relates to a rheology enhancer or crystal growth inhibitor compR1sing DPP of the formula la and/or lb. In common practice the rheology enhancers or crystal growth inhibitors are used in compositions compR1sing DPP of the formula la and/or lb and DPP or DPP latent pigment. A further embodiment of the present invention relates to compositions compR1sing DPP of the formula la and/or lb and DPP or DPP latent pigment. The present invention relates further to a method of enhancing rheology or of inhibiting crystal growth which compR1ses incorporating an effective amount of DPP of the formula la and/or lb in DPP or a DPP latent pigment. The molar ratio of DPP of the formula la and/or lb is usally in the range from 0.1 to 20 mol-% based on of DPP of the formula la and/or lb and DPP or DPP latent pigment. Furthermore, the present invention relates to the use of DPP of the formula XXI or XXX or bis-DPP lb, or of a composition compR1sing a DPP of the formula XXI and/or XXX and/or DPP la and/or lb and diketo-diaryl-pyrroiopyrrole (DPP) or a DPP latent pigment, wherein DPPs of formula XXI and la, or XXX and lb are different, for colouR1ng/pigmenting high molecular mass organic mateR1al. The invention additionally relates to a method of colouR1ng/pigmenting high molecular mass organic mateR1al which compR1ses incorporating a colouR1stically effective amount of DPP of the formula XXI or XXX or of bis-DPP lb, or of a composition compR1sing a DPP of the formula XXI and/or XXX and/or DPP la and/or lb and diketo-diaryl-pyrrolopyrrole (DPP) or a DPP latent pigment, wherein DPPs of formula XXI and la, or XXX and lb are different, therein, by conventional methods, as descR1bed, for example, in US 5,200.528. In addition, the invention relates to compositions compR1sing high molecular mass organic mateR1al and DPP of the formula XXI or XXX or bis-DPP of the formula lb. In general the weight ratio of DPP of the formula XXI or XXX or bis-DPP of the formula lb or the compositions of the invention is from 0.01 to 30% by weight, preferably from 0.1 to 10% by weight, based on the high molecular mass organic mateR1al. Another preferred embodiment of the present invention relates to compositions consisting of high molecular mass organic mateR1al and DPP of the formula XXI or XXX or bis-DPP of the formula lb and also compositions consisting of DPP of the formula XXI or XXX or bis-DPP of the formula lb and/or high molecular mass organic mateR1al and/or DPP of the formula la and also compositions consisting of DPP of the formula XXI or XXX and/or high molecular mass organic mateR1al and/or DPPs and also compositions consisting of DPP of the formula XXI or XXX and/or high molecular mass organic mateR1al and/or DPP latent pigments and also compositions consisting of DPP of the formula XXI or XXX^and/or high molecular mass organic mateR1al and/or halo-DPP of the formula lla and also compositions consisting of DPP of the formula lb and/or high molecular mass organic mateR1al and/or halo-DPP of the formula lib. High molecular mass organic mateR1als can be of natural or synthetic oR1G1n. They may, for example, compR1se natural resins or drying oils, rubber or casein, or modified natural substances, such as cellulose ethers or esters, cellulose acetate, cellulose propionate, cellulose acetobutyrate or nitrocellulose, and especially entirely synthetic organic polymers (thermosets and thermoplastics) as obtained by addition polymeR1zation, polycondensation. or polyaddition. From the class of the addition-polymeR1zation resins mention may be made pR1maR1ly of polyolefins, such as polyethylene, polypropylene or polyisobutylene, and also substituted polyolefins, such as addition polymers of vinyi chloR1de, vinyl acetate, styrene, acrylonitR1le, acrylates and/or methacrylates or butadiene, and also addition copolymers of the abovementioned monomers, especially acrylonitR1le-butadiene-styrene (ABS) or ethylene-vinyl acetate (EVA). From the seR1es of the polyaddition resins and polycondensation resins mention may be made of the condensation products of formaldehyde with phenols, known as phenolic resins, and of the condensation products of formaldehyde with urea, thiourea and melamine, known as amino resins, the polyesters used as film-forming resins, both saturated, such as alkyd resins, and unsaturated, such as maleate resins, and also the linear polyesters and polyamides, and silicones. The abovementioned high molecular mass organic mateR1als can be present individually or in mixtures, as plastic masses or melts which can if desired be spun to fibre. They can also be present in the form of their monomers or in the polymeR1zed state in dissolved form as film formers or binders for coating mateR1als or pR1nting inks, such as linseed oil varnish, nitrocellulose, alkyd resins, melamine resins and urea-formaldehyde resins, or acrylic resins. The colouR1ng/pigmentation of the high molecular mass organic substances with the DPPs of the formula XXI or XXX or bis-DPP of the formula lb or compositions of the invention compR1sing them takes place in general with the resultant crude product of the process of the invention, or following appropR1ate conditioning and aftertreatment, for example, in such a way that DPP of the formula XXI or XXX or bis-DPP of the.formula lb or compositions of the invention compR1sing them, as they are or in the form of master batches, are admixed to these substrates using roll mills or mixing or milling apparatus. The coloured/pigmented mateR1al is generally brought into the desired final form by techniques known per se, such as callendeR1ng, compression moulding, extrusion, spreading, pouR1ng or injection moulding. It is often desirable, in order to produce nonR1G1d mouldings or to reduce their bR1ttleness, to add plasticizers to the high molecular mass compounds pR1or to their forming. Examples of such plasticizers are esters of phosphoR1c, phthalic or sebacic acid. The plasticizers can be incorporated into the polymers before or after the incorporation of the colorant. It is also possible, in order to obtain different shades, to add fillers and/or other colouR1ng constituents, such as white, coloured or black pigments in the desired amount to the high molecular mass organic substances in addition to DPPs of the formula XXI or XXX or bis-DPPs of the formula lb. For pigmenting coating mateR1als and pR1nting inks, the high molecular mass organic mateR1als and DPPs of the formula XXI or XXX or bis-DPP of the formula lb or compositions of the invention compR1sing them alone or together with additives such as fillers, other pigments, siccatives or plasticizers are customaR1ly dissolved or finely dispersed in a common organic solvent or solvent mixture. In this context it is possible to follow a procedure whereby the individual components are dispersed or dissolved individually or else two or more are dissolved or dispersed together and only then are all the components combined. The resultant bR1ghtly coloured/pigmented high molecular mass mateR1als, examples being plastics, fibres, coatings and pR1nts, are notable for very high colour strength, high saturation, good dispersibility, high fastness to overcoating, heat, light and weather, and high lustre. The process of the invention allows the preparation of a broad range of thio-substituted DPPs of the formula la, and even of long-chain alkylthio-DPPs and water-soluble DPPs, and also of dithio-bR1dged bis-DPPs of the formula lb. The DPPs of the formula la, the bis-DPPs of the formula lb and the compositions of the invention compR1sing a DPP of formula XXI or XXX are colorants of high lustre and transparency. The DPPs of the formula la and also the compositions of the invention compR1sing a DPP of formula XXI or XXX are particularly suitable for inhibiting crystal growth and enhancing rheology. The novel compounds or compositions and the compounds prepared by the process of this invention have good warp fastness properties in high molecular weight mateR1al, in particular in mateR1al that is processed by the injection moulding process using the novel compounds or compositions. Preferred high molecular weight mateR1als are. for example, polyolefins. The high yields obtained with the process of the invention, and its simplicity, which permits operation without elevated pressure and without catalysts, moreover, are a guarantee of good economics. Accordingly, the present invention provides a process for prepaR1ng an alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) of the formula la or a dithio-bR1dged bis-diketo-diaryl-pyrrolopyrrole (bis-DPP) of the formula lb in which in formula la, G is phenyl substituted by at least one arylthio or alkylthio group, and G1is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate, and in formula lb, G5 is a phenylene, Gg is G1, but not G, and G7 is C1-C30 alkylene which can be uninterrupted or interrupted one or more times by heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(O)- or -C(0)-NH- and can be substituted or unsubstituted, C5-C12 cycloalkylene or phenylene, each of which can be substituted or unsubstituted by reacting two haloaryls with a dithiol or dithiolate, which compR1ses reacting a thiol or thiolate with a halo-diketo-diaryl-pyrrolopyrrole ("halo-DPP") of the formula Ila in which G2 is an unsubstituted or substituted halogenated phenyl group and G3 is G2 or G1, or reacting a dithiol or dithiolate with two halo-diketo-diaryl-pyrrolopyrroles ("halo-DPPs") of the fomiula lib in which Hal is halogen such as fluoR1ne, chloR1ne, bromine or iodine, which reaction is carR1ed out by conventional methods, preferably at a temperature within the range from 323 to 453 K, at the reaction pressure within the range from 70 kPa to 10 Mpa and a reaction time within the range from 15 minutes to 2 days. Examples: Example 1: Reaction of 1-octadecanethiol with diketobis(4-chlorophenyl)pyrrolopyrrole (DPP of the formula XXII. = halo-DPP of the formula lla with 62 = 63 = para-CI-phenyl) 17.19 g (60 mmol) of 1-octadecanethiol dissolved in 60 ml of dimethylacetamide, DMA, are added dropwise under nitrogen to a red suspension of 10.72 g (30 mmol) of DPP XXII and 9.95 g (72 mmol) of potassium carbonate in 260 ml of DMA. The resultant mixture is then heated at 393 K for 24 hours, duR1ng which it turns violet. Workup and isolation: The reaction mixture is cooled to room temperature and then poured into 60 ml of ice water. The aqueous reaction mixture is filtered. The filter residue is washed with methanol and then with water and subsequently dR1ed in vacuo at 353 K. This G1ves 24.37 g (94.7% of theory by weight) of a red pigment. Examples 2-10: see Tables 1,2,3 and 4 below Examples 11-21: The reactions take place in analogy to that of Example 1 but, in contradistinction to Example 1, using instead of the DPP of the formula XXII in Example 11 diketo-4,4'-dibromo(diphenyl)pyrrolopyrrole (DPP of the formula lla with G2 = G3 = para-Br-phenyl); in Examples 12 and 13 diketo-4,4\3,3'-tetrachloro(diphenyl)pyrrolopyrrole (DPP of the formula lla with 62 = 63 = para,meta-dichlorophenyl); in Example 14 diketo-4-chloro(diphenyl)pyrrolopyrrole, (DPP of the formula lla with G2 ^ G1; G2 = para-chlorophenyl and G1= phenyl); in Example 15 diketo-4-chloro-4-methyl(diphenyl)pyrrolopyrrole (DPP of the formula lla with 629^61:62 = para-chlorophenyl and G1= para-methylphenyl); in Example 16 diketo-4-chioro-4-tert-butyl(diphenyl)pyrrolopyrrole (DPP of the formula lla with G2 5^ G1; G2 = para-chlorophenyl and G1= para-tert-butylphenyl); in Example 17 diketo-4-chloro-4-phenyl(diphenyl)pyrrolopyrrole (DPP of the formula lla with 62^61:62 = para-chlorophenyl and G1= para-phenylphenyl); in Example 18 diketo-3-bromo(diphenyl)pyrrolopyrrole (DPP of the formula lla with G2 ^ GuGz = meta-bromophenyl and G1= phenyl); in Examples 19-21 (preparation of bis-DPP) diketo-4-chloro-4-phenyl(diphenyl)pyrrolopyrrole (DPP of the formula lib with G2 = para-chlorophenyl and Ge = phenyl) is employed and in Examples 22-28 the reaction takes place in analogy to that of Example 1 but, in contradistinction to Example 1, using instead of the DPP of the formula XXII in Example 22 (composition compR1sino a halo-DPP XXII and a DPP lla with Gg = G;^ = para- Cl-phenyl) thiol in a substoichiometR1c amount with respect to halo-DPP XXII. and in Example 23 using in this case 1.3-dimethyl-3,4,5,6-tetrahydro-3(1H)pyR1midinone instead of the solvent DMA, and in Examples 24-28 varying the bases. Example 2: The filter residue is taken up in 300 ml of methanol and stirred at room temperature, T 295 K, for 12 h. The methanolic reaction mixture is filtered. The filter residue is washed with water. ''Example 4: The reaction mixture is poured into 600 ml of ice water and neutralized with concentrated hydrochloR1c acid until the pH reaches 7. The aqueous reaction mixture is filtered. The filter residue is washed with methanol and water. ''Example 11: After the filter residue has been washed with methanol and then with water, it is admixed with ethyl acetate, heated to boiling temperature and stirred at this temperature for 2 hours. The reaction mixture is subsequently filtered and the filter residue is dR1ed in vacuo at 343 K. ''' Examples 12 and 13: After the filter residue has been washed with water, it is admixed with ethyl acetate, heated to boiling temperature and stirred at this temperature for 6 hours. The reaction mixture is subsequently filtered and the filter residue is dR1ed in vacuo at 343 K. Examples 19-21: As under but using DMA in this case instead of ethyl acetate. ' Example 22: After the filter residue has been washed with water, it is admixed with 300 ml of methanol/water (1:1) and stirred at room temperature. The reaction mixture is subsequently filtered and the filter residue is washed with 300 ml of methanol and then with 300 ml of water and subsequently dR1ed in vacuo at 343 K. WE CLAIM: 1. A process for prqjaring an alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) of the formula la or a dithio-bridged bis-diketo-diaryl-pyrrolopyrrole (bis-DPP) of the formula lb in which in formula la, G is phenyl substituted by at least one arylthio or alkylthio group, and G1 is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate, and in formula lb, G5 is a phenylene, G6 is Gi, but not G, and G7 is C1-C30 alkylene which can be uninterrupted or interrupted one or more times by heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(O)- or -C(0)-NH- and can be substituted or unsubstituted, C5-C12 cycloalkylene or phenylene, each of which can be substituted or unsubstituted by reacting two haloaryls with a dithiol or dithiolate, which comprises reacting a thiol or thiolate with a halo-diketo-diaryl-pyrrolopyrrole ("halo-DPP") of the formula Ila in which G2 is an unsubstituted or substituted halogenated phenyl group and G3 is G2 or G1, or reacting a dithiol or dithiolate with two halo-diketo-diaryl-pyrrolopyrroles ("halo-DPPs") of the formula 11b in which Hal is halogen such as fluorine, chlorine, bromine or iodine, which reaction is carried out by conventional methods, preferably at a temperature within the range from 323 to 453 K, at the reaction pressure within the range from 70 kPa to 10 Mpa and a reaction time within the range from 15 minutes to 2 days. 2. The process according to claim 1, wherein the thiol or thiolate employed is a compound of the formula Ilia or a dithiol or dithiolate of the formula Illb in which Ri can be C1-C30oalkyl which can be uninterrupted or interrupted one or more times by heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(0)- or -C(0)-NH-, and can be substituted or unsubstituted, or can be C5-C12cycloalkyl or phenyl, each of which can be substituted or unsubstituted, and R2 is hydrogen, a cation ("M") of an alkali metal, or an organic nitrogen base, and G7 can be Ci-Caoalkylene which can be uninterrupted or interrupted one or more times by heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(O)-or -C(0)-NH-, and can be substituted or unubstituted, or can be C5-C12cycloalkylene or phenylene, each of which can be substituted or imsubstituted. in which E is -0-, -S-, -NH-, -C(0)0-, -0C(0)-, -(CO)NH., -NHC(O)-, and R12 is a single-bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -CH=N-, -N=N-, -0-, -S-, -SO-, -SO2- or -NR3-. The process according to claim 1 or 4, wherein G2 is a compound of the formula XV in which Hal is fluorine, chlorine, bromine or iodine and R13 and R14 independently of one another are, for example, hydrogen, CN, CF3, C1-C5alkyl, C5-C6cycloalkyl, -E-C1-C18alkyl, phenyl, S-Ri, amides, such as -CONR3R4 or amides of the formulae XVI to XIX or amides of nitrogen-containing heterocycles such as 1-carbonyl-imidazole, -pyrazole, -triazole, -pyrrole, -pyrrolidine, -benzimidazole or -benzoatriazole, or halogen such as fluorine, chlorine, bromine or iodine. The process according to one of claims 1 to 5, wherein the reaction is conducted in the presence of a known base. The process according to one of claims 1 to 6, wherein the reaction is conducted in the presence of a solvent. An alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) of in which R15, R16, R20 and R21, independently of one another are hydrogen or R13 or R14, and G4 is a carbocyclic or heterocyclic radical, with the proviso that (a) R, in formula XXI is not phenyl if R15 and R16 are hydrogen and G4 is phenyl, and (b) R1 in formula XXX is not phenylene(C1-C4alkyl) or C1-C12alkyl if R15,R16,R20 and R21 are hydrogen, and G5 is a phenylene, G6 is a carbocyclic or heterocyclic radical, and G7 is alkylene, cycloalkylene or phenylene. A composition comprising a DPP of the forumla XXI and/or XXX according to claim 8 and DPP la and/or lb and diketo-diaryl-pyrrolopyrrole (DPP) or a DPP latent pigment, wherein DPPs of formula XXI and la, or XXX and lb are different. A composition comprising a DPP of the formula XXI or XXX or bis-DPP of the formula lb according to claim 8 and a high molecular mass organic material. A process for preparing an alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) substantially as herein described. An alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) substantially as herein described. A composition comprising a DPP substantially as herein described.

Full Text

The present invention relates to an improved process for preparing atkyltliio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrroles (DPPs) of the formula la and dithio-bridged bis-diketo-diaryl-pyrrolopyrroles (bis-DPPs) of the formula lb

in which in formula la
G is phenyl substituted by at least one arylthio or aikylthio group, and
G1is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate,
and
in formula lb
Gs is a phenylene, Ge is G1 but not G, and G7 is alkylene or phenylene, by reacting two
haloaryls with a dithiol or dithiolate.
The invention additionally relates to novel, arylthio- or alkylthio-substituted DPPs, their use, and compositions comprising the DPPs of the invention.
US 4,579,949 and US 4,490,542 describe the preparation of DPPs substituted by at least one thioether group by reacting arylthio- or alkylthio-substituted benzonitriles with succinic esters. Disadvantages are the low yields in the case of long-chain alkylthio-DPPs and the impossibility of obtaining water-soluble compounds.
The reaction of DPP pigments with thiols to give aikylthio- or arylthio-substituted DPPs gives incomplete conversions owing to the poor solubility of these pigments.
Chemistry Letters 1978.13-14 discloses that unactivated haloaryls can be substituted only in the presence of catalysts.

It was therefore an object of the invention to provide an improved process for preparing alkylthio- and/or arylthio-substituted DPPs which permits in particular the preparation of water-soluble compounds and long-chain alkylthio-DPPs. In particular, the process should be operable without high pressures and the use of catalysts. In addition, the economics of the process should be guaranteed by high yields. Furthermore, the invention was to provide novel, thioether-substituted diketo-diaryl-pyrrolopyrroles and also dithioether-bridged bis-DPPs which can be used in compositions with high molecular mass organic material, in particular as colorants. In addition, the thioether-substituted DPPs should be able to be used, in particular, as crystal growth inhibitors or rheology enhancers.
Accordingly, we have found the process defined at the outset, which involves reacting a thiol or thiolate with a halo-diketo-diaryl-pyrrolopyrrole ("halo-DPP") of the formula lla
" 0
■*
in which Hal is halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or
bromine and. with particular preference, chlorine,
Hal being, in particular, in the para position of the phenylene.
Customarily, the reaction is started by bringing the thiol and/or thiolate or the dithiol and/or the dithiolate into contact with the halo-DPP lla or lib by conventional methods, for example by mixing the starting materials or by dropwise addition of one starting material to the other.

To prepare the compounds of the formula la the molar ratio of thiol to halo-DPP of the formula lla is generally chosen to be within the range from 0.1:1 to 20:1. preferably in the range from 2:1 to 5:1 and, with particular preference, in the range from 2.1:1 to 2.7:1, and, to prepare the compounds of the formula lb, the molar ratio of dithiol to halo-DPP of the formula lib is generally chosen to be in the range from 0.5:1 to 20:1, preferably in the range from 0.5:1 to 5:1 and. with particular preference, in the range from 1:1 to 2.7:1.
Preferably, the reaction temperature is chosen to be within the range from 323 to 453 K, preferably in the range from 333 to 433 K, with particular preference in the range from 343 to 423 K and, with very particular preference, in the range from 343 to 413 K.
The reaction pressure is chosen to be generally within the range from 70 kPa to 10 f^Pa, preferably from 90 kPa to 5 MPa; atmospheric pressure is particularly preferred.
The reaction time depends generally on the reactivity of the starting materials, the chosen reaction temperature and the desired conversion. The reaction time is customarily chosen to be within the range from 15 minutes to 2 days.
In one preferred embodiment the reaction is conducted under an inert gas atmosphere using for this purpose preferably nitrogen or noble gases such as helium or argon. Particular preference is given to reaction in a nitrogen atmosphere.
In addition, the reaction can be carried out with or without solvent, with preference being given to reaction in a solvent. Preferred solvents are organic solvents or solvent mixtures such as aprotic, especially non-aqueous aprotic, solvents. Aprotic solvents may be apolar, such as benzene, chlorobenzene and chlorinated hydrocarbons, or polar. The latter are particularly preferred. Examples of polar aprotic solvents which can be used are amides such as hexamethyl-phosphoramide. carboxamides such as N,N'-dimethylformamide and N.N'-dimethylacetamide, or lactams such as N-methylpyrrolidone, N-methyl-2-piperidone, 1,3-dimethyl-3.4,5,6-tetrahydro-3(1H)pyrimidinone or N-methyl-4-piperidone, or urea bases such as N,N' -dimethylethyleneurea, N,N'-dimethyl-propyleneurea. and also acetonitrile, sulfolane, dimethyl sulfoxide, or aromatic solvents such as nitrobenzene.

Preference is given to N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-3,4,5,6-tetrahydro-3(1H)pyrimidinone or N-methyl-pyrrolidone.
The weight ratio of halo-DPP lla or halo-DPP lib to the solvent lies in general within the range from 0.5 to 10% by weight, with particular preference in the range from 1 to 5% by weight and, with very particular preference, in the range from 2 to 3% by weight.
In another preferred embodiment the reaction is conducted in the presence of a base. Examples of suitable bases are alkali metal carbonates, for example Na2CO3 or K2CO3, alkali metal hydrogencarbonates, for example NaHCOa or KHCO3, alkali metal hydroxides, for example NaOH or KOH. alkali metals, such as sodium or potassium, and also aromatic bases, such as pyridine, N,N'-dimethylaminopyridine or quinoline. Preference is given to non-aqueous alkali metal bases and to aromatic bases, particular preference to non-aqueous alkali metal carbonates or alkali metal hydrogencarbonates, and very particular preference to anhydrous K2CO3.
The molar ratio of base to thiol or thiolate lies customarily within the range from 0.5:1 to 5:1, preferably in the range from 1:1 to 4:1 and, with particular preference, in the range from 1:1 to 3:1, and the molar ratio of base to dithiol or dithiolate lies customarily within the range from 1:1 to 10:1, preferably within the range from 1:1 to 5:1 and. with particular preference, in the range from 1:1 to 4:1.
In a preferred embodiment of the process of the invention the reaction is
■4
conducted in the presence of a solvent or solvent mixture and a base.
If desired, the reaction can also be conducted in the presence of catalysts, especially transition metal catalysts, examples being tetrakis(triphenyl-phosphine)palladium(O), -nickel(O), and -platinum(O), and -ruthenium(ll) chloride. Preferably, the reaction is conducted without a catalyst.

If a catalyst is used, it is generally employed in a proportion within the range from 0.001 to 10% by weight, based on halo-DPP of the formula lla or lib, and preferably from 0.5 to 7% by weight and. with particular preference, from 2 to 5% by weight based on the total amount of reactants.
The reaction mixture can be worked up by conventional methods, for example by filtration and subsequent washing of the filter residue and subsequent optional drying. The product may be an individual compound or a mixture of differently substituted compounds of the formula la, or a mixture consisting of halo-DPP lla and a compound of the formula la, or else a mixture consisting of halo-DPP lib and a compound of the formula lb and/or la.
In accordance with observations made to date the thiol or thiolate employed can comprise any known thiols or thiolates, examples being substituted or unsubstituted aryl or alkyl thiolates, it being possible for the latter to be branched or straight-chain, uninterrupted, or interrupted one or more times by heteroatoms.
In a preferred embodiment a thiol or thiolate of the formula ilia or a dithiol or dithiolate of the formula lllb is used.

in which
Ri can be C1-C30alkyi which can be uninterrupted or intermpted one or more times
by heteroatoms, such as -0- or -S-, or by -NH-, -C(0)0-, -Q-C(O)- or -C(0)-NH-,
and can be substituted or unsubstituted, or
can be C5-Ci2cycloalkyl or phenyl, each of which can be substituted or
unsubstituted, and
R2 is hydrogen, a cation ("M") of an alkali metal, or an organic nitrogen base, and
G7 can be C1-C30alkylene which can be uninterrupted or interrupted one or more
times by heteroatoms. such as -0- or -S-. or by -NH-. -C(0)0-. -O-C(O)- or -C(0)-
NH-. and can be substituted or unsubstituted, or

can be C5-C12cycloalkylene or phenylene, each of which can be substituted or unsubstituted.
C1-C30aikyl is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,
sec-amyl. tert-amyl, hexyl, 2.2-dimethylbutyi, heptyl, octyl, 2-ethylhexyl, 1,1',3,3'-
tetramethyibutyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl. octadecyl, eicosyl, heneicosyl,
docosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl or nonacosyl,
preference being given to C1-C18alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl, tert-amyl, hexyl, 2,2-dimethylbutyl, heptyl,
octyl, 2-ethylhexyl, 1,1\3,3'-tetramethylbutyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl and
octadecyl
and particular preference to C8-C18alkyI such as octyl, 2-ethylhexyl, 1,V,3,3'-tetramethylbutyl,
nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or
octadecyl
and very particular preference to C12-C18alkyl such as dodecyl. tridecyl, tetradecyl,
pentadecyl. hexadecyl, heptadecyl or octadecyl;
particular preference is also given to C1-C8alkyI such as methyl, ethyl, propyl, isopropyl,
n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl, tert-amyl. hexyl. 2,2'-dimethyIbutyl,
heptyl. octyl, 2-ethylhexyl and 1,1',3,3'-tetramethylbutyL
C1-C30alkylene is methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene. sec-amylene, tert-amylene, hexylene, 2,2'-dimethylbutylene, heptylene, octylene, 2-ethylhexylene, 1,1',3,3'-tetramethylbutylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, eicosylene, heneicosylene, docosylene, tetracosylene. pentacosylene, hexacosylene. heptacosylene, octacosylene or nonacosylene,
preference being given to C1-C18alkylene such as methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, sec-amylene, tert-amylene, hexylene, 2,2'-dimethylbutylene, heptylene. octylene, 2-ethylhexylene, 1,1'.3,3'-tetramethylbutylene, nonylene, decylene, dodecylene. tetradecylene, hexadecylene or octadecylene, and
particular preference to C8-C18alkylene such as octylene, 2-ethylhexylene, 1.1'.3,3'-tetramethylbutylene, nonylene. decylene, dodecylene, tetradecylene, hexadecylene or octadecylene;

in addition, particular preference is given to C1-C8alkylene such as methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, sec-amylene, tert-amylene, hexylene, 2,2'-dimethylbutylene, heptylene. octylene, 2-ethyl-hexylene or 1,1',3,3'-tetramethylbutylene.
C8-C18cycloalkyI is for example cyclopentyl, cyclohexyl, cycioheptyl or cyclooctyl, preferably C5-C6cycloalkyi such as cyclopentyl or cyclohexyl.
C5-C12cycloalkylene is for example cyciopentylene, cyclohexylene, cycloheptylene or cyclooctylene, preferably C5-C6cycloalkylene such as cyciopentylene or cyclohexylene.
Alkyl radicals or aikylene radicals of at least two carbon atoms, represented by Ri or Gy, can be interrupted one or more times by for example -0-, -NH-, -C(0)0-, -O-C(O)-, -C(0)-NH-; preference is given to -C(0)0- or -0- and very particular preference to the -C(0)0-internjpted alkyl radical -CH2-C(0)0-CH2CH3, or the singly -0-interrupted alkyl radical such as -CH2-CH2-O-CH2-CH3, or the doubly -0-interrupted alkyl radical such as -CH2-CH2-O-
Cn2—CH2—O—CH2—CH3.
In addition, the alkyl or cycloalkyi radicals or the phenyl radical of R1 can be substituted by, for example, the following radicals:
C1-C18alkyl, OR3. S-R3. C(0)R3. COOR3, -OCOR3. SO3R3, SO2R3. PO3R3. Si(0R)3, a salt radical such as S-M, 0-M, COOM, SO3M, POafvl, P(R3)3' X', P((R3)2 R4 )3' X", NO2,
N(R3)3' X", N((R3)2 R4 )3' X' or a nitrogen-containing radical, in which
R3 and R4 independently of one another are hydrogen. C1-C18alkyI, especially methyl,
ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-amyl, tert-amyl.
hexyl or 2,2-dimethylbutyl, or are C5-C6cycloalkyI or unsUbstituted or Ry-substituted
phenyl,
M is a cation of an alkali metal, preferably sodium or potassium.
X" is a halide, such "as fluoride, chloride, bromide or iodide, and
R7 is hydrogen, halogen such as F, CI, Br, I or is C1-C8alkyl or unsubstituted or NR3R4-
substituted C5-C6cycloalkyl.
Preferred OR3 is OH. and preferred S-R3 is SH.

Preferred radicals COOR3 are COOH. COOCH3, COOC2H5, COOC4H9, COOC5H11. and
preferred -OCOR3 is -0-CO-C(CH2)-CH3.
Preferred radicals SO3R3 are SO3H, S03(C5H4)R7. SOaCCsHg), SO3CH3, SO3C2H5. and
preferred radicals SO2R3 are S02(C5H4)R7. S02(C5H4) or SO2CH3.
Preferred radicals PO3R3 are PO3H, P03(C5H4)R7 or PO3CH3,
Preferred nitrogen-containing radicals are selected from the group consisting of NR3R4.
especially NH2. NHR3 or N(R3 R4), with particular preference being given to substituted alky!
radicals, such as (R3 R4)N-{C1-C3oalkyl)-, especially (CH3)2N-C2H5-,
further preferred nitrogen-containing radicals are selected from the group consisting of
CONHNH2, CONHR3, NHCOR3. NCO and
a heterocyclic radical and
a compound selected from the group of the formulae IV to IX

selected in particular from the group of the compounds of the formulae IV and V,
in which
t'
R5 independently of R? has the same definition as R7. and
Re is a direct bond, -CH2-. -CH(CH3)-, -C(CH3)2-, -CH=N-. -N=N-, -0-, -S-, -SO-.
-SO2- or -NR3-. and r is zero or an integer from 1 to 17.
Furthermore, the alkyiene, cycloaikylene or phenylene radical of G7 can be substituted by, for example, the following radicals:
halogens such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine and. with particular preference, chlorine;

-E-C1C18alkyI,
in which
E is -0-, -S-, -NH-, -C(0)0-, -00(0)-. -NHC(O)-, -C(0)NH-;
CN, NO2, CFa or c1-C18alkyl, which can be uninterrupted or interrupted one or more times by
heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(O)- or -C(0)-NH-.
If E is -0-. then -O-Ci-CisalkyI can be methoxy, ethoxy, n-propoxy, isopropoxy, hexadecyloxy or octadecyloxy, preferably methoxy or ethoxy and, with very particular preference, methoxy.
If E is -S-, then -S-C1-C18alkyl can be methylmercapto, ethylmercapto, n-propylmercapto, isopropylmercapto, hexadecylmercapto or ocatdecylmercapto, preferably methylmercapto or ethylmercapto and, with very particular preference, methylmercapto.
If E is -NH-, then -NH-C1-C18aikyi can be methylamine, ethylamine, n-propylamine, isopropylamine, hexadecylamine or octadecylamine, preferably methylamine or ethylamine and, with very particular preference, methylamine.
If E is -C(0)0- then -C(0)0-C1-C18alkyI can be methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, hexadecoxycarbonyl or octadecoxycarbonyi, preferably methoxycarbonyl or ethoxycarbonyl and, with very particular preference, methoxycarbonyl.
If E is -0C(0)- then -0C(0)-C1-C18alkyl can be a methyl, ethyl, n-propyl, isopropyl, hexadecyl or octadecyl ester radical, preferably a methyl or ethyl ester radical and, with very particular preference, a methyl ester radical.
If E is -C(0)NH- then -C(0)NH-C1-C18alkyl can be a methyl-, ethyl-, n-propyl-. isopropyl-, hexadecyl- or octadecylaminocarbonyl radical, preferably a methyl- or ethylaminocarbonyl radical and, with very particular preference, methyl-aminocarbo'nyl radical.
If E is -NHC(O)- then -NHC(0)-C1-C18alkyl can be a methyl-, ethyl-, n-propyl-, isopropyl-, hexadecyl- or octadecylcarbonylamino radical, preferably a methyl- or

ethylcarbonylamino radical and, with very particular preference, methylcarbonylamino radical.
Preferred substituted alkylene radicals for G7 are symmetrically substituted radicals such as
-(CH2)m-CH(C1-C30alkyl)-(CH2)m or -(CH2)m-C(C1-C30alkyl)2-(CH2)m. in which
m is an integer in the range from 1 to 14, with particular preference an integer in the range
from 3 to 8.
Preferred substituted phenylene radical G7 possesses one or two substituents such as
halogen, C1-C18alkyi, -O-C1-C18alkyI, -S-C1-C18alkyI, -NH-C1-C18alkyI, CN, NO2 or CF3, where
the substituents can be identical or different.
Heterocyclic radical is, for example, a five-membered nitrogen-containing heterocyclic radical such as imidazolyl, pyrazolyl, triazolyl, pyrrolyl, pyrrolidinyl, oxazolyl or thiazolyl, a six-membered nitrogen-containing heterocyclic radical such as piperazinyl, piperidinyl, pyridinyl or morpholinyl, or a bicyclic radical which possesses a fused-on five-membered nitrogen-containing heterocycle and a six-membered aromatic ring, such as benzoxazolyl, indolyl, benzothiazolyl, benzimidazolyl or benzotriazolyl.
Examples of suitable organic nitrogen bases for R2 are pyridine, morpholine, N,N'-dimethylaminopyridine and quinoline.
Particular preference is given to thiols such as C1-C18alkyl-SH, especially H-S-(CH2)n-CH3, in which n is an integer from 8 to 17, H-S-CH2COOC2H5. H-S-CH2CH2COOC2H5, H-S-(para-methylphenyl), H-S-(para-hydroxyphenyl), and also H-S-(CH2)nrNR3R4 in which n1 is an integer from 8 to 18, H-S-{CH2)2N(CH3)2, and also thiolates such as sodium salts or potassium salts of 'S-id-Ciealkyl), 'S-(CH2)2-OH. •S-CH2COOC2H5. "S-Cpara-methylphenyl), ■S-(para-hydroxyphenyl) or ■S-(CH2)2N(CH3)2.
Particularly preferred dithiols are -S-(C1-C18alkylene)-S-. especially -S-(C3-C8alkylene)-S-, such as -S-(CH2)3-S-, -S-(CH2)4-S-, -S-(CH2)5-S-, -S-(CH2)6-S-, -S-(CH2)7-S- or -S-(CH2)8-S-. and very particularly preferred dithiols are -S-(CH2)3-S-. -S-(CH2)5-S- or -S-(CH2)6-S-.
The thiols, dithiols or thiolates, dithiolates of the formula I11a or 111b are obtainable commercially or by known methods for preparing thiols, dithiols or thjolates. dithiolates

(Houben-Weyl, Methoden der organischen Chemie, Volume E 11, pp. 32-63, Georg Thieme Verlag, Stuttgart, New York, 1985; and J.L. Wardell, "Preparation of Thiols", in S. PATAI (ed.), The chemistry of the thiol group, pp. 163-269. John Wiley & Sons, London. New York, 1974).
In the process of the invention a halo-DPP of the formula Ha is used in which G2 is a halogenated phenyl group and G3 is G2 or G1i, and G3 is preferably G2 or a carbocyclic or heterocyclic radical and with particular preference is G2; in other words, the halo-DPP of the formula lla in that case is a symmetrically substituted halo-DPP.
If G3 or Ge is G1, then the radical involved can also be a heterocyclic radical which corresponds to the above definition of heterocyclic radicals and is additionally pyrimidine, thiophene or furan, or else the radical involved can be a carbocyclic group of the formula XI, XllorXlil

in which
R8. R9. Rio and R11
independently of one another are hydrogen, halogen such as fluorine, chlorine, bromine or iodine or C1-C18alkyI,

and in particular hydrogen,C1-C5alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl. sec-butyl, tert-butyl, n-pentyl, sec-amyl or tert-amyl. or halogen such as CI or Br, and R12 is a single bond, -CH2-. -CHCCH3)-, -C(CH3)2-. -CH=N-, -N=N-. -0-, -S-, -SO-, -SO2- or -NR3-.

With particular preference, halo-DPP of the formula lib together with G6 is an organic radical such as

in which
R40 and R41 independently of one another are hydrogen, halogen such as fluorine, chlorine,
bromine or iodine, or C1-C18alkyI, -E-C1-C18alkyi. -CN. -NO2 or trifluoromethyl.
With very particular preference G6 is an organic radical such as

in which
R42 and R43 independently of one another are hydrogen, chlorine, methyl, tert-butyl or -CN.
In one preferred embodiment the halogenated phenyl group G2 employed is a compound of the formula XIV

in which Hal is halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine. With particular preference, halogen is in the para position.
If desired, the halogenated phenyl group G2 can be a compound of the formula XV

and can carry further substituents, R13 or R14, where R13and R14 independently of one another are, for example,
hydrogen, CN, CF3, C1-C5aikyl, C5-C6cycloalkyi, -E-C1-C18alkyI, phenyl, S-Ri, amides
such as -CONR3R4 or amides of the formulae XVI to XIX

or amides of nitrogen-containing heterocycles such as 1-carbonyl-imidazole, -pyrazoie. -triazole, -pyrrole, -pyrrolidine, -benzimidazole or -benzotriazole, or halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.
Preferably, R13 and R14 are in the meta positions.
In a further preference, R14 is hydrogen and R13 is one of the above substituents other than hydrogen, preferably in the meta position.
In another preferred embodiment the halogenated phenyl group G2 is of the formula XX

in which Hal is preferably fluorine, chlorine, bromine or iodine and. with particular preference, chlorine or bromine.

Halo-DPPs II with correspondingly substituted groups are known, for example, from patents US 5,484,943, US 5,616,725 or US 5,200,528 or are obtainable in accordance with US 4,579,949.
A further embodiment of the present invention relates to new DPPs of the formulae XXI and XXX

in which R15. R16. R20 and R21 independently of one another are hydrogen or R1aor Ru, and G4 is a carbocyclic or heterocyclic radical, with the proviso that (a) R1 in formula XXI is not phenyl if R15 and R16 are hydrogen and G4 is phenyl, and (b) R1 in formula XXX is not phenylene(CrC4alkyl) or C1-C12alkyl if R15. R16. R20 and R21 are hydrogen, and G5 is a phenylene, G6 is a carbocyclic or heterocyclic radical, and G7 is alkylene, cycloalkylene or phenylene.
Preferred DPPs of the fonnula XXI or XXX are those in which R1 is mono- or polysubstituted or unsubstituted C1-C30alkyl or a phenyl radical.
With particular preference. R15, R1. R20 and R21 are hydrogen and R1 is -C1-C18alkyl. such as C4alkyl, C6alkyI, C9alkyl. C12alkyl or C6alkyl. and also -(para-

phenylene)-OH, -CH2CH2OH, -CH2C(0)0-CH2CH3, -(CH2)2C(0)0-CH2CH3 -(C1-C30alkylene)-N(R3,R4) such as -(C2H5)-N(CH3)2.
Particular preference is G1ven to compounds of the formula lb in which G5 is 1,4-phenylene and G7 is n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene or n-octyiene, or substituted or unsubstituted phenylene and Geis unsubstituted or substituted phenyl.
Very particular preference is G1ven to compounds of the formula lb in which G5 is 1,4-phenylene and G? is n-propylene, n-butylene, n-pentylene, n-hexyiene. n-heptylene or n-octylene and Ge is unsubstituted phenyl.
Very particular preference is G1ven to compounds of the formula XXXI or XXXII

A further embodiment of the present invention relates to compositions compR1sing a DPP of the formula la and a halo-DPP of the formula lla, obtainable by the process of the invention using a substoichiometR1c amount of thiol or thiolate of the formula Ilia. Preferably, the thiol or thiolate of the formula Ilia is employed in a molar ratio that is within the range from 0.1 to 49%, based on the total amount of thiol or thiolate of the formula Il1a and halo-DPP of the formula lla.

A further embodiment of the process of the invention relates to compositions compR1sing at least two differently substituted DPPs of the formula la. These compositions are obtainable either by reacting at least two differently substituted halo-DPPs of the formula lla with a thiol or thiolate of the formula Ilia or, conversely, by reacting at least two differently substituted thiols or thiolates of the formula Ilia with a halo-DPP of the formula lla.
The molar ratio of thiol or thiolate of the formula Ilia to differently substituted halo-DPPs of the formula lla, or of differently substituted thiols or thiolates of the formula Ilia to halo-DPP of the formula lla, is generally chosen to be within the range from 20:0.1 to 1:1, preferably in the range from 10:1 to 5:1 and, with very particular preference, within the range from 5:1 to 5:2.
The molar ratio of the differently substituted halo-DPPs of the formula lla to one another is generally chosen to be within the range from 0.1 to 99.9 mol-%, based on the total amount of differently substituted halo-DPPs of the formula lla, and is preferably in the range from 20 to 80 mol-% and, with particular preference, in the range from 40 to 60 mol-%.
The molar ratio of differently substituted thiols or thiolates of the formula Ilia to one another is generally chosen to be within the range from 0.1 to 99.9 mol-%. based on the total amount of differently substituted thiols or thiolates of the formula Ilia, is preferably within the range from 20 to 80 mol-% and, with particular preference, in the range from 40 to 60 mol-%.
The invention relates, furthermore, to compositions compR1sing a DPP of the formula XXI and/or XXX and/or DPP la and/or lb and diketo-jdiaryl-pyrrolopyrrole (DPP) or a DPP latent pigment, wherein DPPs of formula XXI and la, or XXX and lb are different. DPP latent pigments are descR1bed, for example, in US 5,616.725. In a preferred embodiment, the molar ratio of DPP of the formula XXI and/or XXX to DPP. DPP of the formula la or lb. or DPP latent pigment is chosen to be within the range from 0.1 to 99.9 mol-%, based on the total amount of DPP of the formula XXI or XXX, DPP or DPP latent pigment, more preferably from 20 to 80 mol-% and. with particular preference, from 40 to 60 mol-%.

These compositions of the invention can be prepared by customary methods, for example, by mixing the individual components with one another in accordance with the customary methods, in analogy, for example, to the method descR1bed in US 5.200.528.
The DPPs can be prepared by customary methods as descR1bed in US 5,200,528. Similarly, the DPP latent pigments can be prepared in analogy to the method descR1bed in US 5,561,232.
Furthermore, the invention relates to the use of DPP of the formula la and/or lb as rheology enhancers or as crystal growth inhibitors.
A further embodiment of the present invention relates to the use of DPPs of the formula XXI or XXX as rheology enhancers or as crystal growth inhibitors.
In addition, the invention relates to a rheology enhancer or crystal growth inhibitor compR1sing DPP of the formula la and/or lb.
In common practice the rheology enhancers or crystal growth inhibitors are used in compositions compR1sing DPP of the formula la and/or lb and DPP or DPP latent pigment.
A further embodiment of the present invention relates to compositions compR1sing DPP of the formula la and/or lb and DPP or DPP latent pigment.
The present invention relates further to a method of enhancing rheology or of inhibiting crystal growth which compR1ses incorporating an effective amount of DPP of the formula la and/or lb in DPP or a DPP latent pigment.
The molar ratio of DPP of the formula la and/or lb is usally in the range from 0.1 to 20 mol-% based on of DPP of the formula la and/or lb and DPP or DPP latent pigment.
Furthermore, the present invention relates to the use of DPP of the formula XXI or XXX or bis-DPP lb, or of a composition compR1sing a DPP of the formula XXI and/or XXX and/or DPP la and/or lb and diketo-diaryl-pyrroiopyrrole (DPP) or a DPP latent pigment, wherein DPPs of

formula XXI and la, or XXX and lb are different, for colouR1ng/pigmenting high molecular mass organic mateR1al.
The invention additionally relates to a method of colouR1ng/pigmenting high molecular mass organic mateR1al which compR1ses incorporating a colouR1stically effective amount of DPP of the formula XXI or XXX or of bis-DPP lb, or of a composition compR1sing a DPP of the formula XXI and/or XXX and/or DPP la and/or lb and diketo-diaryl-pyrrolopyrrole (DPP) or a DPP latent pigment, wherein DPPs of formula XXI and la, or XXX and lb are different, therein, by conventional methods, as descR1bed, for example, in US 5,200.528.
In addition, the invention relates to compositions compR1sing high molecular mass organic mateR1al and DPP of the formula XXI or XXX or bis-DPP of the formula lb.
In general the weight ratio of DPP of the formula XXI or XXX or bis-DPP of the formula lb or the compositions of the invention is from 0.01 to 30% by weight, preferably from 0.1 to 10% by weight, based on the high molecular mass organic mateR1al.
Another preferred embodiment of the present invention relates to compositions consisting of
high molecular mass organic mateR1al and DPP of the formula XXI or XXX or bis-DPP of the
formula lb and also
compositions consisting of DPP of the formula XXI or XXX or bis-DPP of the formula lb
and/or high molecular mass organic mateR1al and/or DPP of the formula la and also
compositions consisting of DPP of the formula XXI or XXX and/or high molecular mass
organic mateR1al and/or DPPs and also
compositions consisting of DPP of the formula XXI or XXX and/or high molecular mass
organic mateR1al and/or DPP latent pigments and also
compositions consisting of DPP of the formula XXI or XXX^and/or high molecular mass
organic mateR1al and/or halo-DPP of the formula lla and also
compositions consisting of DPP of the formula lb and/or high molecular mass organic
mateR1al and/or halo-DPP of the formula lib.
High molecular mass organic mateR1als can be of natural or synthetic oR1G1n. They may, for
example, compR1se natural resins or drying oils, rubber or casein, or modified natural
substances, such as cellulose ethers or esters, cellulose acetate, cellulose propionate,
cellulose acetobutyrate or nitrocellulose, and especially entirely synthetic organic polymers
(thermosets and thermoplastics) as obtained by addition polymeR1zation, polycondensation.

or polyaddition. From the class of the addition-polymeR1zation resins mention may be made pR1maR1ly of polyolefins, such as polyethylene, polypropylene or polyisobutylene, and also substituted polyolefins, such as addition polymers of vinyi chloR1de, vinyl acetate, styrene, acrylonitR1le, acrylates and/or methacrylates or butadiene, and also addition copolymers of the abovementioned monomers, especially acrylonitR1le-butadiene-styrene (ABS) or ethylene-vinyl acetate (EVA).
From the seR1es of the polyaddition resins and polycondensation resins mention may be made of the condensation products of formaldehyde with phenols, known as phenolic resins, and of the condensation products of formaldehyde with urea, thiourea and melamine, known as amino resins, the polyesters used as film-forming resins, both saturated, such as alkyd resins, and unsaturated, such as maleate resins, and also the linear polyesters and polyamides, and silicones.
The abovementioned high molecular mass organic mateR1als can be present individually or in mixtures, as plastic masses or melts which can if desired be spun to fibre.
They can also be present in the form of their monomers or in the polymeR1zed state in dissolved form as film formers or binders for coating mateR1als or pR1nting inks, such as linseed oil varnish, nitrocellulose, alkyd resins, melamine resins and urea-formaldehyde resins, or acrylic resins.
The colouR1ng/pigmentation of the high molecular mass organic substances with the DPPs of the formula XXI or XXX or bis-DPP of the formula lb or compositions of the invention compR1sing them takes place in general with the resultant crude product of the process of the invention, or following appropR1ate conditioning and aftertreatment, for example, in such a way that DPP of the formula XXI or XXX or bis-DPP of the.formula lb or compositions of the invention compR1sing them, as they are or in the form of master batches, are admixed to these substrates using roll mills or mixing or milling apparatus. The coloured/pigmented mateR1al is generally brought into the desired final form by techniques known per se, such as callendeR1ng, compression moulding, extrusion, spreading, pouR1ng or injection moulding. It is often desirable, in order to produce nonR1G1d mouldings or to reduce their bR1ttleness, to add plasticizers to the high molecular mass compounds pR1or to their forming. Examples of such plasticizers are esters of phosphoR1c, phthalic or sebacic acid. The plasticizers can be incorporated into the polymers before or after the incorporation of the colorant. It is also

possible, in order to obtain different shades, to add fillers and/or other colouR1ng constituents, such as white, coloured or black pigments in the desired amount to the high molecular mass organic substances in addition to DPPs of the formula XXI or XXX or bis-DPPs of the formula lb.
For pigmenting coating mateR1als and pR1nting inks, the high molecular mass organic mateR1als and DPPs of the formula XXI or XXX or bis-DPP of the formula lb or compositions of the invention compR1sing them alone or together with additives such as fillers, other pigments, siccatives or plasticizers are customaR1ly dissolved or finely dispersed in a common organic solvent or solvent mixture. In this context it is possible to follow a procedure whereby the individual components are dispersed or dissolved individually or else two or more are dissolved or dispersed together and only then are all the components combined.
The resultant bR1ghtly coloured/pigmented high molecular mass mateR1als, examples being plastics, fibres, coatings and pR1nts, are notable for very high colour strength, high saturation, good dispersibility, high fastness to overcoating, heat, light and weather, and high lustre.
The process of the invention allows the preparation of a broad range of thio-substituted DPPs of the formula la, and even of long-chain alkylthio-DPPs and water-soluble DPPs, and also of dithio-bR1dged bis-DPPs of the formula lb. The DPPs of the formula la, the bis-DPPs of the formula lb and the compositions of the invention compR1sing a DPP of formula XXI or XXX are colorants of high lustre and transparency. The DPPs of the formula la and also the compositions of the invention compR1sing a DPP of formula XXI or XXX are particularly suitable for inhibiting crystal growth and enhancing rheology. The novel compounds or compositions and the compounds prepared by the process of this invention have good warp fastness properties in high molecular weight mateR1al, in particular in mateR1al that is processed by the injection moulding process using the novel compounds or compositions. Preferred high molecular weight mateR1als are. for example, polyolefins. The high yields obtained with the process of the invention, and its simplicity, which permits operation without elevated pressure and without catalysts, moreover, are a guarantee of good economics.

Accordingly, the present invention provides a process for prepaR1ng an alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) of the formula la or a dithio-bR1dged bis-diketo-diaryl-pyrrolopyrrole (bis-DPP) of the formula lb

in which in formula la, G is phenyl substituted by at least one arylthio or alkylthio group, and G1is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate, and in formula lb, G5 is a phenylene, Gg is G1, but not G, and G7 is C1-C30 alkylene which can be uninterrupted or interrupted one or more times by heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(O)- or -C(0)-NH- and can be substituted or unsubstituted, C5-C12 cycloalkylene or phenylene, each of which can be substituted or unsubstituted by reacting two haloaryls with a dithiol or dithiolate, which compR1ses reacting a thiol or thiolate with a halo-diketo-diaryl-pyrrolopyrrole ("halo-DPP") of the formula Ila

in which G2 is an unsubstituted or substituted halogenated phenyl group and G3 is G2 or G1, or reacting a dithiol or dithiolate with two halo-diketo-diaryl-pyrrolopyrroles ("halo-DPPs") of the fomiula lib

in which Hal is halogen such as fluoR1ne, chloR1ne, bromine or iodine, which reaction is carR1ed out by conventional methods, preferably at a temperature within the range from 323 to 453 K, at the reaction pressure within the range from 70 kPa to 10 Mpa and a reaction time within the range from 15 minutes to 2 days.

Examples:
Example 1: Reaction of 1-octadecanethiol with diketobis(4-chlorophenyl)pyrrolopyrrole (DPP
of the formula XXII. = halo-DPP of the formula lla with 62 = 63 = para-CI-phenyl)
17.19 g (60 mmol) of 1-octadecanethiol dissolved in 60 ml of dimethylacetamide, DMA, are added dropwise under nitrogen to a red suspension of 10.72 g (30 mmol) of DPP XXII and 9.95 g (72 mmol) of potassium carbonate in 260 ml of DMA. The resultant mixture is then heated at 393 K for 24 hours, duR1ng which it turns violet. Workup and isolation:
The reaction mixture is cooled to room temperature and then poured into 60 ml of ice water. The aqueous reaction mixture is filtered. The filter residue is washed with methanol and then with water and subsequently dR1ed in vacuo at 353 K. This G1ves 24.37 g (94.7% of theory by weight) of a red pigment.
Examples 2-10: see Tables 1,2,3 and 4 below
Examples 11-21:
The reactions take place in analogy to that of Example 1 but, in contradistinction to
Example 1, using instead of the DPP of the formula XXII
in Example 11 diketo-4,4'-dibromo(diphenyl)pyrrolopyrrole (DPP of the formula lla with G2 =
G3 = para-Br-phenyl);
in Examples 12 and 13 diketo-4,4\3,3'-tetrachloro(diphenyl)pyrrolopyrrole (DPP of the
formula lla with 62 = 63 = para,meta-dichlorophenyl);
in Example 14 diketo-4-chloro(diphenyl)pyrrolopyrrole, (DPP of the formula lla with G2 ^ G1;
G2 = para-chlorophenyl and G1= phenyl);
in Example 15 diketo-4-chloro-4-methyl(diphenyl)pyrrolopyrrole (DPP of the formula lla with
629^61:62 = para-chlorophenyl and G1= para-methylphenyl);
in Example 16 diketo-4-chioro-4-tert-butyl(diphenyl)pyrrolopyrrole (DPP of the formula lla
with G2 5^ G1; G2 = para-chlorophenyl and G1= para-tert-butylphenyl);
in Example 17 diketo-4-chloro-4-phenyl(diphenyl)pyrrolopyrrole (DPP of the formula lla with
62^61:62 = para-chlorophenyl and G1= para-phenylphenyl);
in Example 18 diketo-3-bromo(diphenyl)pyrrolopyrrole (DPP of the formula lla with G2 ^ GuGz = meta-bromophenyl and G1= phenyl);

in Examples 19-21 (preparation of bis-DPP) diketo-4-chloro-4-phenyl(diphenyl)pyrrolopyrrole
(DPP of the formula lib with G2 = para-chlorophenyl and Ge = phenyl) is employed and
in Examples 22-28 the reaction takes place in analogy to that of Example 1 but, in
contradistinction to Example 1, using instead of the DPP of the formula XXII
in Example 22 (composition compR1sino a halo-DPP XXII and a DPP lla with Gg = G;^ = para-
Cl-phenyl) thiol in a substoichiometR1c amount with respect to halo-DPP XXII. and
in Example 23 using in this case 1.3-dimethyl-3,4,5,6-tetrahydro-3(1H)pyR1midinone instead
of the solvent DMA, and
in Examples 24-28 varying the bases.

Example 2: The filter residue is taken up in 300 ml of methanol and stirred at room
temperature, T 295 K, for 12 h. The methanolic reaction mixture is filtered. The filter residue
is washed with water.
''Example 4: The reaction mixture is poured into 600 ml of ice water and neutralized with
concentrated hydrochloR1c acid until the pH reaches 7. The aqueous reaction mixture is
filtered. The filter residue is washed with methanol and water.
''Example 11: After the filter residue has been washed with methanol and then with water,
it is admixed with ethyl acetate, heated to boiling temperature and stirred at this temperature
for 2 hours. The reaction mixture is subsequently filtered and the filter residue is dR1ed in
vacuo at 343 K.
''' Examples 12 and 13: After the filter residue has been washed with water, it is admixed
with ethyl acetate, heated to boiling temperature and stirred at this temperature for 6 hours.
The reaction mixture is subsequently filtered and the filter residue is dR1ed in vacuo at 343 K.
Examples 19-21: As under but using DMA in this case instead of ethyl acetate.
' Example 22: After the filter residue has been washed with water, it is admixed with
300 ml of methanol/water (1:1) and stirred at room temperature. The reaction mixture is

subsequently filtered and the filter residue is washed with 300 ml of methanol and then with 300 ml of water and subsequently dR1ed in vacuo at 343 K.

WE CLAIM:
1. A process for prqjaring an alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) of the formula la or a dithio-bridged bis-diketo-diaryl-pyrrolopyrrole (bis-DPP) of the formula lb

in which in formula la, G is phenyl substituted by at least one arylthio or alkylthio group, and G1 is G or a carbocyclic or heterocyclic radical, by reacting a haloaryl with a thiol or thiolate, and in formula lb, G5 is a phenylene, G6 is Gi, but not G, and G7 is C1-C30 alkylene which can be uninterrupted or interrupted one or more times by heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(O)- or -C(0)-NH- and can be substituted or unsubstituted, C5-C12 cycloalkylene or phenylene, each of which can be substituted or unsubstituted by reacting two haloaryls with a dithiol or dithiolate, which comprises reacting a thiol or thiolate with a halo-diketo-diaryl-pyrrolopyrrole ("halo-DPP") of the formula Ila

in which G2 is an unsubstituted or substituted halogenated phenyl group and G3 is G2 or G1, or reacting a dithiol or dithiolate with two halo-diketo-diaryl-pyrrolopyrroles ("halo-DPPs") of the formula 11b

in which Hal is halogen such as fluorine, chlorine, bromine or iodine, which reaction is carried out by conventional methods, preferably at a temperature within the range from 323 to 453 K, at the reaction pressure within the range from 70 kPa to 10 Mpa and a reaction time within the range from 15 minutes to 2 days.
2. The process according to claim 1, wherein the thiol or thiolate employed is a compound of the formula Ilia or a dithiol or dithiolate of the formula Illb

in which Ri can be C1-C30oalkyl which can be uninterrupted or interrupted one or more times by heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(0)- or -C(0)-NH-, and can be substituted or unsubstituted, or can be C5-C12cycloalkyl or phenyl, each of which can be substituted or unsubstituted, and R2 is hydrogen, a cation ("M") of an alkali metal, or an organic nitrogen base, and G7 can be Ci-Caoalkylene which can be uninterrupted or interrupted one or more times by heteroatoms, such as -O- or -S-, or by -NH-, -C(0)0-, -O-C(O)-or -C(0)-NH-, and can be substituted or unubstituted, or can be C5-C12cycloalkylene or phenylene, each of which can be substituted or imsubstituted.

in which E is -0-, -S-, -NH-, -C(0)0-, -0C(0)-, -(CO)NH., -NHC(O)-, and R12 is a single-bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -CH=N-, -N=N-, -0-, -S-, -SO-, -SO2- or -NR3-.
The process according to claim 1 or 4, wherein G2 is a compound of the formula XV

in which Hal is fluorine, chlorine, bromine or iodine and R13 and R14 independently of one another are, for example, hydrogen, CN, CF3, C1-C5alkyl, C5-C6cycloalkyl, -E-C1-C18alkyl, phenyl, S-Ri, amides, such as -CONR3R4 or amides of the formulae XVI to XIX

or amides of nitrogen-containing heterocycles such as 1-carbonyl-imidazole, -pyrazole, -triazole, -pyrrole, -pyrrolidine, -benzimidazole or -benzoatriazole, or halogen such as fluorine, chlorine, bromine or iodine.

The process according to one of claims 1 to 5, wherein the reaction is conducted in the presence of a known base.
The process according to one of claims 1 to 6, wherein the reaction is conducted in the presence of a solvent.
An alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) of

in which R15, R16, R20 and R21, independently of one another are hydrogen or R13 or R14, and G4 is a carbocyclic or heterocyclic radical, with the proviso that (a) R, in formula XXI is not phenyl if R15 and R16 are hydrogen and G4 is phenyl, and (b) R1 in formula XXX is not phenylene(C1-C4alkyl) or C1-C12alkyl if R15,R16,R20 and R21 are hydrogen, and G5 is a phenylene, G6 is a carbocyclic or heterocyclic radical, and G7 is alkylene, cycloalkylene or phenylene.

A composition comprising a DPP of the forumla XXI and/or XXX according to claim 8 and DPP la and/or lb and diketo-diaryl-pyrrolopyrrole (DPP) or a DPP latent pigment, wherein DPPs of formula XXI and la, or XXX and lb are different.
A composition comprising a DPP of the formula XXI or XXX or bis-DPP of the formula lb according to claim 8 and a high molecular mass organic material.
A process for preparing an alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) substantially as herein described.
An alkylthio- and/or arylthio-substituted diketo-diaryl-pyrrolopyrrole (DPP) substantially as herein described.
A composition comprising a DPP substantially as herein described.

Documents:

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in-pct-2000-577-che-abstract.pdf

in-pct-2000-577-che-claims.pdf

in-pct-2000-577-che-correspondence others.pdf

in-pct-2000-577-che-correspondence po.pdf

in-pct-2000-577-che-description complete.pdf

in-pct-2000-577-che-form 1.pdf

in-pct-2000-577-che-form 3.pdf

in-pct-2000-577-che-form 5.pdf

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Patent Number

243726

Indian Patent Application Number

IN/PCT/2000/577/CHE

PG Journal Number

45/2010

Publication Date

05-Nov-2010

Grant Date

02-Nov-2010

Date of Filing

27-Dec-2000

Name of Patentee

CIBA HOLDING INC

Applicant Address

Klybeckstrasse 141 CH-4002 Basel

Inventors:

#	Inventor's Name	Inventor's Address
1	HAO, Zhimin	Gstaltenrainweg 75 CH-4125 Riehen
2	ROCHAT, Alain, Claude	Route de Schiffenen 40 CH-1700 Fribourg
3	SCHLÖDER-TEBALDI, Nancy	Chemin des Glycines 6 CH-1753 Matran

PCT International Classification Number

C08K 5/3415

PCT International Application Number

PCT/EP1999/002513

PCT International Filing date

1999-04-14

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	915/98	1998-04-22	Switzerland