CZ20003883A3 - Process for preparing alkylthio- and/or arylthio-substituted diketo diaryl pyrrolopyrroles - Google Patents

Abstract

Preparation of alkylthio- and / or alkylthio-substituted diketondiarylpyrrolopyrroles of the formula Ia and bisdetetiarylpyrrolopyrroles with a dithio-bridging group of formula (Ib), by reacting haloaryl with thiol or thiolate for the preparation of a compound of formula (Ia) or by reacting two haloaryls with dithiol or dithiolate v in the case of the preparation of a compound of the general formula (Ib) consists in reacting a thiol or thiolate s haloalkoetodiarylpyrrolopyrrole of formula IIa, or dithiol or dithiolate is reacted with two haloalkoetodiarylpyrrolopyrroles of general formula IIb as i new diketodiarylpyrrolopyrroles and also bisdetodiarylpyrrolopyrroles and compositions comprising diketodiarylpyrrolopyrroles of formula Ia prepared according to the invention and their use.

Description

Process for preparing alkylthio- and / or arylthio-substituted diketodiarylpyrrolopyrrols

178145 / KB

- J (f? L

Technical field

The invention relates to an improved process for the preparation of alkylthione or / and arylthio-substituted diketodiarylpyrrolopyrrols (DPP) of the formula Ia and bis-diketodiarylpyrrolopyrroles containing a dithio-bridged group of the formula Ib

Ib, substituted at least wherein in said formula Ia

G represents a phenyl group with one arylthio or alkylthio group,

G is G or a carbocyclic or heterocyclic group, and in said Formula Ib

G, represents a phenylene group,

G 1 is G, but not G a

G is an alkylene or phenylene group, by reacting a haloaryl with a thiol or a thiolate to prepare a compound of formula (Ia) or by reacting two haloaryl with a dithiol or a dithiolate

Preparation of a compound of formula (1b).

The invention further relates to novel arylthio-substituted diketodiarylpyrrolopyrrols, their use and compositions containing these diketodiarylpyrrolopyrrols.

BACKGROUND OF THE INVENTION

U.S. Pat. Nos. 4,579,949 and 4,490,542 disclose the preparation of diketodiarylpyrrolopyrrols substituted with at least one thioether group by reacting arylthio- or alkylthio-substituted benzonitriles with succinic esters. The drawbacks of this preparation are low yields for long chain alkylthiodiketodiarylpyrrolopyrrols and the inability to obtain water-soluble compounds.

Reaction of diketodiarylpyrrolopyrrole pigments with thiols to obtain alkylthio- or arylthio-substituted diketodiarylpyrropyrroles results in incomplete conversions due to the poor solubility of these pigments.

Chemistry Letoers 1978, 13-14 states that unactivated haloaryls can only be substituted in the presence of catalysts.

It is therefore an object of the invention to provide an improved process for preparing alkylthio- and / or arylthio-substituted particularly enabled long chain compounds.

The invention of diketodiarylpyrrolopyrroles of diketodiarylpyrrolopyrroles which would produce water-soluble alkylthiodiketodiarylpyrrolopyrrols. This process should be particularly practicable without the use of high pressures and catalysts. Moreover, the economics of such a process should be guaranteed by high yields. In addition, it should provide novel thioether-substituted as well as bis-diketodiarylpyrrolopyrroles containing a dithioether bridge that would be high molecular weight dyes. In addition to being used in a composition with substances, particularly as thioether substituted, organic diketodiarylpyrrolopyrroles should be capable of being used in particular as crystal growth inhibitors or rheology enhancers.

SUMMARY OF THE INVENTION

Accordingly, a process as defined above has now been found which comprises reacting a thiol or thiolate with a halo-diketodiarylpyrrolopyrrole (halo-DPP) of the formula IIIa.

wherein G ₂ is an unsubstituted or substituted, halogenated phenyl group and G 1 is G _z or G 1, or a reaction of a dithiol or dithiolate with two halodiketodiarylpyrrolopyrroles of the general formula Hb

lib,

Hal in which Hal is a halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, especially chlorine, with Hal particularly being in the para position of the phenylene group.

4

Typically, the reaction is initiated by contacting the thiol and / or thiolate or dithiol and / or dithiolate with a halodiketodiarylpyrrolopyrrole of formula IIa or IIb in a conventional manner, for example by mixing said starting materials or adding one starting material dropwise to another starting material.

In the preparation of the compounds of the formula Ia, the molar ratio of thiol to the halodiketodiarylpyrrolopyrrole of the formula I is generally used in the range from 0.1: 1 to 20: 1, preferably in the range from 2: 1 to 5: 1, particularly in the range from 2: 1: 1 to 2.7: 1, while the molar ratio of dithiol to halodiketodiarylpyrrolopyrrole of formula IIb is generally in the range of 0.5: 1 to 20: 1, preferably in the range of 0.5: 1 to 5: 1, especially in the range from 1: 1 to 2.7: 1.

The reaction temperature is preferably used in the range of 323 to 453 K, preferably in the range of 333 to 433 K. In particular, in the range of 343 to 423 K and most preferably in the range of 343 to 413 K.

The reaction pressure is selected from 70 to 10 MPa, preferably from 90 to 5 MPa, particularly preferably at atmospheric pressure.

The reaction time depends on the reactivity of the starting materials, the reaction temperature selected and the desired conversion rate. This reaction time is usually selected from 15 minutes to 2 days.

According to a preferred embodiment of the invention, the reaction is carried out under an inert gas atmosphere, preferably nitrogen or a noble gas such as helium or argon. Particularly preferably, said reaction is carried out under a nitrogen atmosphere.

In addition, the reaction may be carried out in the presence or absence of a solvent, more preferably the reaction is carried out in the presence of a solvent. Preferred solvents are organic solvents or solvent mixtures, such as aprotic solvents, especially non-aqueous aprotic solvents. Aprotic solvents may be apolar solvents such as benzene, chlorobenzene and chlorinated hydrocarbons, or polar solvents. Particularly preferred solvents are polar solvents. Examples of useful polar aprotic solvents include amides such as hexamethylphosphoramide, carboxamides such as α, N'-dimethylacetamide, or, for example, N-methylpyrrolidone,

1,3-dimethyl-3,4,5,6-tetrahydro-3 (1H) pyrimidinone or N-methyl-4-piperidone, or urea bases such as Ν, N'-dimethylethylene urea, Ν, N'-dimethylpropylene urea as well as acetonitrile , sulfolane, dimethylsulfoxide, or aromatic solvents such as nitrobenzene.

Ν, N'-dimethylformamide lactams such as

N-methyl-2-piperidone

Preferred solvents are Ν, N'-dimethylformamide, Ν, N'-dimethylacetamide, dimethylsulfoxide,

1,3-dimethyl-3,4,5,6-tetrahydro-3 (1H) pyrimidinone or N-methylpyrrolidone.

The weight ratio of the halodiketodarylpyrrolopyrrole of formula IIa or the halodiketodiarylpyrrolopyrrole of formula IIb to the solvent is generally in the range from 0.5 to 10% by weight, more preferably in the range from 1 to 5% by weight. and in particular the ratio is in the range of 2 to 3% by weight.

In a further preferred embodiment of the invention said reaction is carried out in the presence of a base. Examples of suitable bases include alkali metal carbonates such as sodium carbonate or potassium carbonate, bicarbonates, and bicarbonates. Alkali metals such as sodium bicarbonate or potassium bicarbonate, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metals such as sodium or potassium, as well as aromatic bases such as pyridine,

Ν, N'-dimethylaminopyridine or quinoline. Preferred bases are non-aqueous alkali metal bases and aromatic bases, especially non-aqueous alkali metal carbonates or non-aqueous alkali metal hydrogencarbonates, with anhydrous potassium carbonate being a particularly preferred base.

The molar ratio of base to thiol or thiolate generally lies in the range of 0.5: 1 to 5: 1, preferably in the range of 1: 1 to 4: 1, especially in the range of 1: 1 to 3: 1, while the molar ratio of base to dithiol or dithiolate generally ranges from 1: 1 to 10: 1, preferably from 1: 1 to 5: 1, and in particular from 1: 1 to 4: 1.

In a preferred embodiment of the process according to the invention, the reaction is carried out in the presence of a solvent or a mixture of solvents and a base.

If desired, the reaction can also be carried out in the presence of catalysts, in particular transition metal catalysts, examples of which are tetrakis / triphenylphosphine) palladium (0), tetrakis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) platinum (0) and tetrakis (triphenylphosphine) ruthenium (II) chloride. Preferably, said reaction is carried out without a catalyst.

When the catalyst is used, it is generally used in an amount ranging from 0.001 to 10% by weight, based on the weight of the halodiketodiarylpyrrolopyrrole of formula IIa or IIb, and preferably in the range of 0.5 to 7% by weight, especially A range of 2 to 5% by weight based on the total amount of the reactants is used.

The reaction mixture may be worked up by conventional means, for example by filtration and subsequent washing of the residue on the filter and optionally drying of the product obtained. The product obtained can be either a single compound or a mixture of differently substituted compounds of formula (Ia) or a mixture of halodiketodiarylpyrrolopyrrole (IIa) and a compound of formula (Ia) or a mixture of halodiketodiarylpyrrolopyrrole (IIb) and a compound of formula (Ib) and / or Ia.

It has been found that the thiol or thiolate used may be of any known thiol or thiolate, examples of which are substituted aryl or alkylthiolates, and it is possible that the latter may contain a straight or branched chain which may in turn be uninterrupted or once or interrupted by heteroatoms. ·

In a preferred embodiment of the process according to the invention, a thiol or thiolate of formula IIIa or a dithiol or dithiolate of formula IIIb is used.

R, -SR ~ lila, R.S-G-SR. Illb in which

R 1 represents an alkyl group having 1 to 30 carbon atoms, which may be uninterrupted or interrupted one or more times by heteroatoms such as -0 or -S-, or -NH-, -C (O) O-, -OC (O) - or

-C (O) -NH-, and may be substituted or unsubstituted, or a cycloalkyl group containing 5 to 12 carbon atoms or m-atoms or a phenyl group, each of which may be unsubstituted or substituted ,

R. represents a hydrogen atom, an alkali metal cation (M)

4i or an organic nitrogen base; and

G- represents an alkylene group containing 1 to 30 carbon atoms, which may be uninterrupted or interrupted one or more times by heteroatoms such as -0 or -S-, or -NH-, -C (O) O-, -OC (O) - or

-C (O) -NH, and may be substituted or unsubstituted, or a C 5 -C 12 cycloalkylene group or a phenylene group, each of which may be substituted or unsubstituted.

C 1 -C 30 alkyl is methyl, ethyl, n-butyl, isopropyl, isobuyl, sec-butyl, n-pentyl, tert-amyl,

2,2-dimethylbutyl, heptyl, 2-ethylhexyl

1,1 ', 3,3'-tetramethylbutyl, nonyl carbon propyl, tert-butyl sec.amyl hexyl group, group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group a heneicosyl group, a docosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group or a nonacosyl group, preferably an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-amyl, tert-amyl, hexyl, 2,2-dimethylbutyl, heptyl, octyl, 2-ethylhexyl, 1, 13,3 ' -tetramethylbutyl, nonyl, sec-butyl n-pentyl, 0 «0 00 T ·» · 99 9 9

9 9 9 »· · 0

0 9 9 9

A group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group and an octadecyl group, particularly preferably an alkyl group containing 8 to 18 carbon atoms, such as an octyl group,

2-ethylhexyl, 1,1 ', 3,3'-tetramethylbutyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl, particularly preferred C 12 -C 18 alkyl, such as dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl, and particularly preferably C 1 -C 8 alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pencyl, sec-amyl, tert-amyl, hexyl, 2,2'- dimethylbutyl, heptyl, octyl, 2- ethylhexyl and 1,1 ', 3m 3'-tetramethylbutyl.

Alkylene-containing atoms are methylene, up to 30 carbon ethylene, propylene, isopropylene, n-butylene, sec-butylene, t-butylene.

n-pentylene, sec-amylene tert-amylene, hexylene

2,2'-aimethylbutylene, heptylene octylene, 2-ethnylhexylene

1,1 ', 3,3'-tetramethylbutylene' group, decylene group, dodecylene tetradecylene group, hexadecylene group, group, group, group, group, group, nonylene group, group, group, group, eicosylene docosylene octadecylene heneicosylene • 9 group, group, 9 · • · ··· 9

an octacosylene group or a nonacosylene group, preferably an alkylene group having 1 to 18 carbon atoms, such as methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, t-butylene, n- pentylene, sec-amylene, tert-amylene, hexylene, 2,2'-dimethylbutylene, heptylene, octylene, 2-ethynylhexylene, 1,1 ', 3,3'-tetramethylbutylene, nonylene a decylene group, a dodecylene group, a tetradecylene group, a hexadecylene group or an octadecylene group, particularly preferably an alkylene group having 8 to 18 carbon atoms, such as octylene, 2-ethylhexylene, 1,13,3'-tetramethylbutylene, nonylene, a decylene group, a dodecylene group, a tetradecylene group a, hexadecylene or octadecylene, and also particularly preferably C 1 -C 8 alkylene, such as methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, target. butylene, n-pentylene, sec-amylene, tert-amylene, hexylene, 2,2'-dimethylbutylene, heptylene, octylene, 2-ethylhexylene or 1,1, 3,3'- a tetramethylbutylene group.

C 5 -C 12 -cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably cycloalkyl having 5 or 6 carbon atoms, such as cyclopentyl or cycloalkyl;

cyclohexyl,

A C 5 -C 12 cycloalkylene group is, for example, a cyclopentylene group, a group, a cycloheptylene group or a group, preferably a cycloalkylene group or 6 carbon atoms, such as a 5-cyclopentylene cyclohexylene or cyclohexylene group.

Alkyl groups containing at least 2 carbon atoms in the meaning of the radicals R or G ₇ may be interrupted by one or more members, such as -0-, -NH-, -C (0) 0-, -0C (0) ~, -C (O) -NK-, preferably -C (O) O or -C- and particularly preferably -C (O) O-, and is preferably a -C (O) O- interrupted alkyl group of formula - CH-C (O) O- CH.CH, or a member of -O- once interrupted by an alkyl group such as a group of the formula -CH.-CH.-O-CH.-CH. i Z Z. 0 'A.

an alkyl group such as -CH .. -CH. -O-CH. -CH. -O-CH. -CH ,.

for example sxupma formulas

In addition, an alkyl, cycloalkyl or phenyl group represented by R may be substituted by groups such as: alkyl having 1 to 18 carbon atoms, OR, SR _? , C (0) R ,, C00R ₅ -OCORj, _S0.R; , 'SO.R _? , PO-R, Si (OR), salt groups such as SM, O-M, p (r) / x *, p ((r ₃ ) ₂ rj; x \ no., N (r) .) cx-,

COOM, SO ₃ M, PO ₃ M, N ((R ₃ ). R.) / X 'or a nitrogen-containing group wherein

R and R independently of one another are hydrogen, C 1 -C 18 alkyl, in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert. butyl, n-pentyl, sec-amyl, tert-amyl, hexyl or

A 2,2-dimethynylbutyl group or a cycloalkyl group containing 5 or β carbon atoms or an unsubstituted or R-substituted phenyl group,

M is an alkali metal cation, preferably sodium or potassium cation,

X represents a halide anion, for example a fluoride, chloride, bromide or iodide anion, and

R is hydrogen, halogen, such as fluorine, chlorine, bromine or iodine, alkyl of 1-8 carbon atoms or unsubstituted or R_ _{NR-substituted} cycloalkyl group containing 5 or 6 carbon atoms.

Preferably OR- is OH, while S-R- is preferably SH.

Preferably, the COOR group is COOH, COOCH-, COOC.H, COOCJH. COOC, H. and -OCOR, preferably is -C-CC-C (CH 3 -C 11).

Preferably SO, R 30 represents H, SO, _(C H) R _7, SO _(C H _5), SO, CHL, SO, CH _R, while the SO ₂ R, _and preferably represents S0 (C HJ R _7, SO ₂ (C ₌ H), or _SO; CH ,.

The group PO, R _{3 is} preferably PO-H, PO ₃ (C ₅ H ₇ R ₇ or PO, CH 3).

Preferred nitrogen-containing groups are selected from the group consisting of NR, R 1, especially NH ₂ , NHR, or N (R Y), which groups are preferably substituted alkyl groups such as a (R, R) N-alkyl group, wherein the alkyl moiety contains 1 to 30 carbon atoms, and in particular the (CH -) - NC.H.- group, wherein the preferred nitrogen-containing groups are further preferably selected from the group consisting of CONHNH ₂ , CONHR, NHCOR, and a heterocyclic group; A group selected from the group consisting of groups of formulas (IV) to (IX)

in particular a group of formulas (IV) and (V), wherein in said 5 X.

R _R R independently represents any of the meanings given for R_,

R 1 represents a direct bond, -C 1 L-, -CH (CH 2) -, C 1 H 3, -,

-CH = N-, N = N-, -O-, -S-, -SO-, -SO ₄ - or -NR ₄ -an is zero or an integer from 1 to 17.

In addition, an alkylene, cycloalkylene or phenylene group of G _{7 may be} substituted, for example, by one of the following:

halogen atoms such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, and especially chlorine,

-E-alkyl having an alkyl radical of 1 to 18 carbon atoms, and E is -O-, -S-, -NH-,

-C (O) O-, -OC (O) -, -NHC (O) -, -C (O) NH- and

CN, NO ₂ , CF, or an alkyl group containing 1 to 18 · · · · · ···

............

carbon atoms, which may be uninterrupted or interrupted one or more times by heteroatoms such as -O- or

-S- or -NH-, -C (O) O-, -O-C (O) - or -C (O) -NH- groups.

In the case where E is -O-, then -O-alkyl having an alkyl radical of 1 to 18 carbon atoms may be methoxy, ethoxy, n-propoxy, isopropoxy, hexadecyloxy or an octadecyloxy group, preferably a methoxy group or an ethoxy group, and in particular a methoxy group.

When E is -S-, then -S-alkyl having an alkyl radical of 1 to 18 carbon atoms may be methylmercapto, ethylmercapto, n-propylmercapto, isopropylmercapto, hexadecylmercapto or an octadecylmercapto group, preferably a methylmercapto group or an ethylmercapto group, and in particular a methylmercapto group.

When Ξ is -NH-, then -NH-alkyl having an alkyl radical of 1 to 18 carbon atoms, it may be methylamino, ethylamino, n-propylamino, isopropylamino, hexadecylamino or octadecylamino, preferably methylamino. or ethylamino, and especially methylamino.

When E is -O (O) O-, then -C (O) O-alkyl having an alkyl moiety of 1 to 18 carbon atoms may be methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropylcarbonyl , hexadecoxycarbonyl or octadecoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl, and in particular methoxycarbonyl.

When E is -OC (O) -, then -OC (O) -alkyl having an alkyl radical of 1 to 18 carbon atoms may be methyl, ethyl, η-propyl, isopropyl, hexadecyl or an octadecyl ester group, preferably a methyl or ethyl ester group, in particular a methyl ester group.

When E is -C (O) NH-, then -C (O) NH-alkyl having an alkyl radical of 1 to 18 carbon atoms may be a methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl , hexadecylaminocarbonyl or octadecylaminocarbonyl, preferably methylaminocarbonyl or ethylaminocarbonyl, especially methylaminocarbonyl.

When Ξ is -NHC (O) -, then -NHC (O) -alkyl having up to 18 carbon atoms in the alkyl moiety may be methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, isopropylcarbonylamino, hexadecylcarbonylamino or ocadecylcarbonylamino, preferably methylcarbonylamino or ethylcarbonylamino, especially methylcarbonylamino.

Preferred substituted alkylene groups as defined by G are symmetrically substituted groups such as

- (C1-L) _T- CH (C1-C4-alkyl) - (CEL) - or a group

- _(CH2) -C _{(C 3 C} -C -alkyl) ₂ - (CH ₂₎ in which m is an integer ranging from 1 to 14, preferably an integer in the range 3 to 8

• · · «· ························································. ··

Preferred substituted phenylene radical representing ₇ G substituent contains one or two identical or different substituents chosen from halogen atoms, alkyl having 1 to 18 carbon atoms, -O-alkyl group in which the alkyl radical contains 1 to 18 carbon atoms -S-alkyl in which the alkyl radical contains 1 to 18 carbon atoms, -NH-alkyl in which the alkyl radical contains 1 to 18 carbon atoms, CN, NO. and CF ..

A heterocyclic group is, for example, a 5-membered aluminum-containing heterocyclic group such as an imidazolyl group, a pyrazolyl group, a triazolyl group, a pyrrolyl group, a pyrrolidinyl group, an oxazolyl group or a thiazolyl group, a six membered nitrogen-containing group such as piperazinyl, pyrididinyl or a morpholinyl group, or a bicyclic group which comprises in a fused configuration a five-membered nitrogen-containing heterocyclic aromatic ring group, a benzoxazolyl group, a benzothiazolyl group, a benzimidazolyl group or a benzotriazolyl group.

a six-membered group such as an indolyl group,

Examples of suitable organic nitrogen bases R are pyridine, morpholine, N, N'-dimethylaminopyridine and quinoline.

Particular preference is given to thiols, such as alkyl-SH, in which the alkyl radical contains 1 to 18 carbon atoms, in particular HS- (CH3 + -CH3), wherein n represents an integer from 8 to 17, HS-CH.COOC. H, HS-CH, _H-C CH.COOC HS- (para-methylphenyl) as well as HS- (CH -NR _R4, wherein nl is an integer of 8 to 18, HS- (CH. ₁₂ N (CH ₃ ) ₂ as well as thiolates, such as sodium or potassium salts with an anion S-alkyl, in which the alkyl moiety contains 1 to C atoms, S- (para-methylphenyl), -S - (CH ₂ ) _£ N (CH ₃ ) ₂ .

'S- (CH.) ₂ -OH,' S-CH ₂ COOC ₂ H ₅ , S- (para-hydroxyphenyl) or

Particularly preferred dithiols are dithiols • S-alkylene-S- in which the alkylene radical contains 1 to 18 carbon atoms, in particular -S-alkylene-S- in which the alkylene radical contains 3 to 8 carbon atoms, such as -S- ( CH.) ₇ -SS- (CH.), -S-,

-S- (CH.), -S

-S- (CH3) _; -SS- (CH _{2) 5} -S-, especially dithiols

-S- (CH3) -S, -S- (CH3) _; -S- or -S- (CH ₂ ), -S-.

The thiols, dithiols, thiolates and dithiolates of formulas IIa and IIIb are either commercially available or obtainable by generally known methods for the preparation of thiols, dithiols, or thiolates and dithiolates (Houben-Weyl, Methoden der organischen Chemie, Vol. Eli, p. 32) -63, Georg Thieme Verlag, Stuttgart, New York, 1985; and JLWardell, Preparation of Thicls, S Patai (ed.), The Chemistry of the Thiol Group, pp. 163-269, John Wiley and Sons, London, New York, 1974).

In the method according halogendiketodiarylpyrrolopyrrol wherein G represents a halogenated phenyl group and G ₃ is G ₂ or G, and G ₂ is preferably a G or a carbocyclic or heterocyclic group, and in particular the present invention applies the general formula Ila in represents

G ₂ ;

it means in my words.

the halodiketodiarylpyrrolopyrrole of formula IIIa in this case is symmetrically halodiketodiarylpyrrolopyrrole.

substituted with a heterocyclic moiety as defined above

In the case where G ₃ or G _t is G., the group may also be,

• · · ·

1S heterocyclic groups, which is additionally a pyrimidine group, a thiophene group or a furan group, or otherwise an appropriate group may be a carbocyclic group of formula XI, XII or XII

XIII wherein in the above general formulas

R., R. ,, R ,,. and R1 independently of one another are hydrogen, halogen, such as fluorine, chlorine, bromine or iodine, or an alkyl group containing 1 to 18 carbon atoms, an -E-alkyl group in which the alkyl radical contains 1 to 18 carbon atoms, -CN, -NO ₄ , trifluoromethyl, cycloalkyl containing 5 or 6 carbon atoms, or a group of formula

And in particular a hydrogen atom, an alkyl group containing 1 to 5 carbon atoms, such as mechyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl a group, a sec-amyl group, or a halogen atom such as a chlorine atom or a bromine atom, and

R., represents a single bond, -CH.-, -CH (CH 2) -, -C (CH ₂ , -CH = N-, -N = N-, -O-, -S-, -SO-, -so _from - or -NR, -.

Particularly preferred is a halodiketodiarylpyrrolopyrrole of the formula IIb in which G 1 is one of the following organic groups

wherein R 1 _: R ₁ and R 2 _; independently of one another represent a hydrogen atom, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group containing 1 to 18 carbon atoms, an -E-alkyl group in which the alkyl radical contains 1 to 18 carbon atoms , -CN, -NO., Or trifluoromethyl.

Particularly preferably, G „organic groups are one of the following wherein R _J2 is hydrogen, tert-butyl

and R1 is independently of one another chlorine, methyl or -CN.

meaning a group,

In a preferred embodiment, the phenyl group XIV is the halogenated G substituent used.

of

Hal

XIV wherein Hal represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom. Preferably, the halogen atom is in the para position.

If desired, the halogenated phenyl group G may be _a group of formula XV

XV additionally bearing R or R substituents _; which, independently of one another, represent a hydrogen atom, a CN group, a trifluoromethyl group, an alkyl group containing 1 to 5 carbon atoms, a cycloalkyl group containing 5 or 6 carbon atoms, an alkyl radical containing a group, the

-Ξ-alkyl having 1 to 18 carbon atoms, S-R, an amide group such as -CONR.R. or the following amide groups of formulas XVI to XIX

or amide groups of nitrogen-containing heterocycles, such as a 1-carbonylimidazole group,

1-carbonylpyrazole, 1-carbonyltriazole, 1-carbonylpyrrole,

1-carbonylpyrrolidine,

1-carbonylbenzimidazole or

A 1-carbonylbenzotriazole group, or a halogen atom such as a fluorine atom, a bromine atom, a chlorine atom or an iodine atom.

Preferably, R., and R. are in meta positions.

Preferably R @ 1 is hydrogen and R @ 1 is any of the above substituents other than hydrogen and in the meta position.

In another preferred embodiment, the halogenated G ₂ substituent of G _{2 is} XX

XX wherein Hal is preferably fluorine, chlorine, bromine or iodine, particularly preferably chlorine or bromine.

Halodiketodiarylpyrrolopyrrols with appropriately substituted groups are known, for example from US Patent Nos. 5,484,943, 5,616,725 or US 5,200,528, or are obtainable by the methods described in US Patent 4,579,949.

A further embodiment of the invention relates to diketodiarylpyrrolopyrrols of formulas XXI and XXX of the novel compounds.

R, S

R, 21

XXX

XXI and the novel bis-diketodiarylpyrrolopyrrols of formula Ib

HN

NH wherein in these formulas, R. ,, R, _R, R _z. and R ₂₁ independently of one another is hydrogen or R. or RG is a carbocyclic or heterocyclic group, with the proviso that a) R. in formula XXI is not a phenyl group when R and R are hydrogen and G_ is a phenyl group, and that

b) R in formula XXX is not a phenylenalkyl group in which the alkyl radical contains 1 to 4 carbon atoms, or an alkyl group containing 1 to 12 carbon atoms in the case R _; , R ₁ , R ₂ and R ₂ represent a hydrogen atom, G 1 represents a phenylene group, G 1. represents a carbocyclic or heterocyclic group and G- represents an alkylene group, a cycloalkylene group or a phenylene group.

Preferred diketodiarylpyrrolopyrroles of formula XXI or XXX are those of formula XXI or XXX.

wherein R ₁ represents a mono- or polysubstituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a phenyl group.

Particularly preferably, R @ 1, R @ 1 and R @ 2 are hydrogen and R @ 1 is C1 -C18 alkyl, such as, for example, C 4 alkyl, C 6 alkyl, C 9 alkyl. atoms or an alkyl group containing 12 carbon atoms, as well as - (para-phenylene) -OH, -CH, CH ₂ OH, -CH.C (O) O-CH ₂ CH ₃ , - (CH). ) O-CH.CH _? - (CH ₂ ) ₂ C (O) O-CH. or an alkylene-N (R-, RJ) group in which the alkylene radical contains 1 to 30 carbon atoms, such as - (C.HJ -N (CH ₂ ) ₂ ).

Particularly preferred are compounds of formula Ib, in which G is 1,4-phenylene and G ₇ is η-β-propylene n-pentylene n-heptylene, n-butylene n-hexylene, n-octylene or substituted or unsubstituted phenylene and G ... represents unsubstituted or substituted phenyl

Particularly preferred are compounds of formula Ib wherein G- is 1,4-phenylene and n-propylene, n-butylene, or n-pentylene n-heptylene n-hexylene means, n-octylene represents an unsubstituted phenyl group

Of particular interest are compounds of formula XXXI or XXXII.

XXXII, wherein in the above formulas R1 is an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms, in particular an alkyl group having 5 to 18 carbon atoms.

A further embodiment of the invention relates to compositions comprising a diketodiarypyrrolopyrrole of formula (1b) and a halodiketodiarylpyrrolopyrrole of formula (IIa) obtainable by the method of the invention using a stoichiometric amount of thiol or thiolate of formula (IIIa). Preferably, the thiol or thiolate of formula IIIa is used in a molar ratio ranging from 0.1 to 49% based on the total amount of the thiol or thiolate of formula IIIa and the halo-di-di-diarylpyrrolopyrrole of formula IIa.

Another embodiment of the invention relates to compositions comprising at least two differently substituted diketodiarylpyrrolopyrroles of the general formula Ia. These compositions are obtainable either by reacting at least two differently substituted halodiketodihydropyrrolopyrrols of formula IIa with a thiol or thiolate of formula IIIa, or vice versa by reacting at least two differently substituted thioles or thiolates of formula IIIa with a halenediketodiarylpyrrolopyrrole of formula IIa.

The molar ratio of the thiol or thiolate of formula IIIa to the differently substituted halodiketodiarylpyrrolopyrroles of formula IIa or the differently substituted thioles or thiolates of formula IIIa to nalogenediketodiarylpyrrolopyrrole of formula IIa is generally selected from 20: 0.1 to 1: 1, preferably from 5 : 1 to 5: 2.

The relative molar ratio of the differently substituted halodiketodiarylpyrrolopyrrols of formula IIa is generally selected from 0.1 to 99.9 mol% based on the total amount of the differently substituted halodiketodiarylpyrrolopyrrols of formula IIa, preferably from 20 to 80 mole percent. % and in particular from 40 to 60 mol%.

The relative mole ratio of the differently substituted thiols or thiolates of formula IIIa is generally selected from 0.1 to 99.9 mol% based on the total amount of the differently substituted thiols or thiolates of formula IIIa, preferably from about 0.1 to 99.9 mol%. 20 to 80 mol% and in particular from 40 to 60 mol%.

The invention further relates to compositions comprising a diketodiarylpyrrolopyrrole of formula XXI and / or XXX and / or a diketodiarylpyrrolopyrrole of formula Ia and / or Ib of an adiketodiarylpyrrolopyrrole or a diketodiarylpyrrolopyrrole latent pigment in which the diketodiarylpyrrolopyrrole is of the general formula XXI and XXa. Diketodiarylpyrrolopyrrole latent pigments are described, for example, in US Patent 5,616,725. In a preferred embodiment, the molar ratio of diketodiarylpyrrolopyrrolu formula XXI and / or XXX to diketodiarylpyrrolopyrrolu, • • · · · · · · • ···· ···· ··· ·· ·· · _r · «·· The diketodiarylpyrrolopyrrols of formula Ia or 1b or the diketodiarylpyrrolopyrrole latent pigment are selected from the range of from 0.1 to 99.9 mol%, based on the total amount of diketodiarylpyrrolopyrrols of the formula XXI or XXX, diketodiarylpyrrolopyrrole or diketodiarylpyrrolopyrrole latent pigment, the ratio being preferably selected from 20 to 80 mol% and in particular from 40 to 60 mol%.

Said compositions of the invention may be prepared by conventional methods, for example by mixing the components together in accordance with conventional procedures, for example by a method analogous to that described in US 5,200,528.

The diketodiarylpyrrolopyrrols may be prepared by conventional methods, for example as described in US Patent 5,200,528. Likewise, diketodiarylpyrrole-pyrrole latent pigments may be prepared in a manner analogous to that described in US 5,561,232.

The invention further relates to the use of diketodiarylpyrrolopyrrols of the general formula Ia and / or 1b as rheology improving agents or as crystal growth inhibitors.

A further embodiment of the invention relates to the use of diketodiarylpyrrolopyrrols of the general formula XXI or XXX as a rheology improving agent or as a crystal growth inhibitor.

The invention further relates to a rheology improving agent or a crystal growth inhibitor comprising a diketodiarylpyrrolopyrrole of formula Ia and / or 1b.

In conventional practice, rheology enhancers or crystal growth inhibitors are used in compositions comprising a diketodiarylpyrrolopyrrole of formula Ia and / or Ib and a diketodiarylpyrrolopyrrole or a diketodiarylpyrrolopyrrole latent pigment.

Another embodiment of the invention relates to compositions comprising a diketodiarylpyrrolopyrrole of formula Ia and / or Ib and a diketodiarylpyrrolopyrrole or diketodiarylpyrrolopyrrole latent pigment.

The invention further relates to a method for improving rheology or inhibiting crystal growth, comprising introducing an effective amount of a diketodiarylpyrrolopyrrole of formula Ia and / or Ib into a diketodiarylpyrrolopyrrole or diketodiarylpyrrolopyrrole latent pigment.

The molar proportion of diketodiarylpyrrolopyrrols of formula Ia and / or Ib is generally selected from 0.1 to 20 mol%, based on the total amount of diketodiarylpyrrolopyrrols of formula Ia and / or Ib and diketodiarylpyrrolopyrroles or diketodiarylpyrrolopyrrole latent pigments.

The invention further relates to the use of diketodiarylpyrrolopyrrole of formula XXI or XXX or bis-diketodiarylpyrrolopyrrole of formula Ib or a composition comprising diketodiarylpyrrolopyrrole of formula XXI and / or XXX and / or diketodiarylpyrrolopyrrole of formula Ia and / or Ib and diketodiarylpyrpyrrolopyrrole XXI and Ia or XXX and Ib are different for dyeing / pigmenting high molecular weight organic materials.

The invention further relates to a dyeing / pigmenting process

characterized in that a color effective amount of a diketodiarylpyrrolopyrrole of formula XXI or XXX or a bis-diketodiarylpyrrolopyrrole of formula Ib or a composition comprising a diketodiarylpyrrolopyrrole of formula XXI or / and XXX and / or diketodiarylpyrrolopyrrole of formula XXI or / and XXX and / or diketodiarylpyrrolopyrrole Ia and / or Ib and diketodiarylpyrrolopyrrole or diketodiarylpyrrolopyrrole latent pigment, wherein the diketodiarylpyrrolopyrroles of formula XXI and Ia or XXX and Ib are different by conventional methods, including, for example, the method described in US 5,200,528.

The invention further relates to compositions comprising a high molecular weight organic substance and a diketodiarylpyrrolopyrrole of formula XXI or XXX or a bis-diketodiarylpyrrolopyrrole of formula Ib.

Generally, the weight fraction of diketodiarylpyrrolopyrrole of formula XXI or XXX or bisdiketodiarylpyrrolopyrrole of formula Ib or compositions of the invention is selected from 0.01 to 30% by weight, preferably from 0.1 to 10% by weight, based on the weight of the high molecular weight organic substances.

Another preferred embodiment of the invention relates to compositions comprising a high molecular weight organic compound and a diketodiarylpyrrolopyrrole of formula XXI or XXX or bis-diketodiarylpyrrolopyrrole of formula IB as well as compositions comprising a diketodiarylpyrrolopyrrole of formula XXI or XXX or bis-diketodiarylpyrrolopyrrole (a) a diketodiarylpyrrolopyrrole of formula (Ia) as well as compositions comprising diketodiarylpyrrolopyrrole of formula (XXI) or (XXX) and / or a high molecular weight organic compound;

φφ φφ

The substance and / or the diketodiarylpyrrolopyrrole and also the compositions containing the diketodiarylpyrrolopyrrole of the general formula XXI or XXX or / or and high molecular weight organic substance and / or diketodiarylpyrrolopyrrole latent pigments as well as compositions containing diketodiarylpyrrolopyrrole of formula XXI or XXX or / and high molecular weight organic substance and / or haloendoketodiarylpyrrolopyrrole of formula IIa and also compositions containing diketodiarylpyrrolopyrrole and / or halo-diketodiarylpyrrolopyrrole of formula IIb.

thermoplastics), polycondensation

Said high molecular weight organic substances may be of natural or synthetic origin. They may, for example, include natural resins, drying oils, rubber or casein, or modified natural substances such as cellulose ethers or esters, cellulose acetate, cellulose propionate, cellulose acetobucyrate or nitrocellulose, and in particular fully synthetic organic polymers (thermosets) which are obtained by addition polymerization Among the addition-polymerization polymers there may be mentioned in particular polyolefins, such as polyethylene, polypropylene or polyisobutylene, as well as substituted polyolefins, such as, for example, addition polymers of vinyl chloride, vinyl acetate, styrene, acrylonitrile, acrylates and / or methacrylates or butadiene. as well as addition copolymers of the abovementioned monomers, in particular acrylonitrile-butadiene-styrene copolymers (ABS) or ethylene-vinyl acetate copolymers (EVA).

Examples of polyaddition resins and polycondensation resins are the formaldehyde condensation products with phenols, known as phenolic resins, and the formaldehyde condensation products with the phenolic resins. 4 urea, thiourea and melamine, known as amine resins, polyesters used as film-forming resins, both saturated, such as alkyd resins. resins, as well as unsaturated, such as maleate resins, as well as linear polyesters and polyamides, as well as silicones.

The abovementioned high molecular weight organic substances may be present individually or in mixtures, such as plastics or melts, which may optionally be spun.

Said substances may also be present in the form of their monomers or in the polymerized state in dissolved form, such as film-forming or coating materials or printing inks such as linseed oil, nitrocellulose, alkyd resins, melamine resins and urea-formaldehyde resins or acrylic resins.

The dyeing / pigmentation of the high molecular weight organic diketodiarylpyrrolopyrroles of formula XXI or XXX or the bis-diketodiarylpyrrolopyrrole of formula Ib or the composition of the invention containing said diketodiarylpyrrolopyrrole is generally carried out using the resulting crude product of the process according to the invention or after appropriate conditioning in which the diketodiarylpyrrolopyrrole of formula XXI or XXX or the bis-diketodiarylpyrrolopyrrole of formula Ib or the composition of the invention containing diketodiarylpyrrolopyrrole as masterbatch is admixed to said roller mill or other type of mill or mixing device. The dyed / pigmented material is converted to the desired final form using techniques known per se, including, for example, calendering, compression molding, extrusion, pouring, or casting into such molds or substrates as described herein.

And / or injection molding. It is often desirable to add plasticizers to the high molecular weight organic materials prior to forming them in order to obtain plasticized products with less stiffness or products having less brittleness. Examples of such plasticizers are esters of phosphoric acid, phthalic acid or sebacic acid. The plasticizers may be incorporated into the polymers before or after incorporation of the colorants. It is also possible, in addition to the diketodiarylpyrrolopyrrole XXI or XXX or the bis-diketodiarylpyrrolopyrrole 1b, to be added in the desired amount to the said high molecular weight substances to achieve different shades of filler and / or color component such as white, color or black pigments.

In order to obtain pigmented paints or printing inks, high molecular weight organic substances, diketodiarylpyrrolopyrroles of formula XXI or XXX or bis-diketodiarylpyrrolopyrroles of formula 1b or compositions of the invention containing said diketodiarylpyrrolopyrroles alone or in combination with additives such as others pigments, driers or plasticizers, dissolved or dispersed in the form of fine particles in a conventional organic solvent or solvent mixture. In this regard, it is also possible to disperse or dissolve the individual components separately or to dissolve or disperse the two or more components separately before mixing all the components as separate solutions or dispersions together.

The resulting brightly colored / pigmented high molecular weight organic substances, for example in the form of plastics, fibers, paints and printing inks, are of excellent quality in terms of intensive coloring, color saturation, good dispersibility, high quality. · Resistance to coating, heat, light and weathering and high resistance ruse.

The process of the invention allows the preparation of a wide range of thio-substituted diketodiarylpyrrolopyrrols of formula Ia and even long-chain alkyl thio-docetodarylpyrrolopyrrols and water-soluble diketodiarylpyrrolopyrroles as well as bis-diketodiarylpyrrolopyrrols of the formula dithio-m-pyrrole. The diketodiarylpyrrolopyrroles of the formula Ia, the bis-diketodiarylpyrrolopyrroles of the formula Ib and the compositions according to the invention containing diketodiarylpyrrolopyrrole of the formulas XXI or XXX are colorants having a high gloss and translucency. The diketodiarylpyrrolopyrrols of formula Ia as well as compositions of the invention containing diketodiarylpyrrolopyrrole of formula XXI or XXX are particularly useful for inhibiting crystal growth and improving rheology. Said novel compounds or compositions prepared by the process of the invention have good antideforming properties in high molecular weight substances, especially in materials which are injection molded using the novel compounds or compositions. Preferred high molecular weight materials are, for example, polyolefins. The high economies of the process and the simplicity of the process, which allows the process to be carried out without the use of elevated pressure and without the use of catalysts, guarantee the good economy of the process according to the invention.

Examples

Example 1

Reaction of 1-octadecanethiol with diketobis- (4-chlorophenyl) pyrrolopyrrole (DPP of formula XXII, = halo-DPP of formula IIa in which:

G. = G. = para-Cl-phenyl)

A solution of 17.19 g (60 mmol) of 1-octadecanethiol in 60 ml of dimethylacetamide (DMA) was added dropwise under a nitrogen atmosphere to a red suspension of 10.72 g (30 mmol) of DPP of formula XXII and 9.95 g (72 mmol). of potassium carbonate in 260 ml of DMA. The mixture was then heated at 393 K for 24 hours, during which time the mixture became violet.

Processing and insulation

The reaction mixture was cooled to room temperature and then poured into 60 mL of ice water. The aqueous reaction mixture was then filtered. The filter residue is washed with methanol and then with water and then dried under vacuum at 353 K. 24.37 g (94.7% of theory) of a red pigment are obtained.

Examples 2 to 10: see Tables 1, 2, 3 and 4 below.

Examples 11 to 21

The procedure is as in Example 1 except that, in contrast to Example 1, instead of DPP XXII, the following is used:

in Example 11 diketo-4,4'-dibromo (diphenyl) diketopyrrolopyrroles (DPP of the formula IIa, wherein G = G ₌ para-Br-phenyl);

in Examples 12 and 13: diketo-4,4 ', 3,3'-tetrachloro (diphenyl) pyrrolopyrrole of general formula IIa in which G ₂ = G ₃ = para, meca-dichlorophenyl);

in Example 14: diketo-4-chloro (diphenyl) pyrrolopyrrole (DPP of Formula IIa in which G ₂ = para-chlorophenyl and G _x = phenyl [G ₂ -G]);

In Example 15: diketo-4-chloro-4-methyl (diphenyl) pyrrolopyrrole (DPP of formula IIa in which G ₂ = parachlorophenyl and G, = paramethylphenyl [G ₂ * G.]);

in Example 16: diketo-4-chloro-4-tert-butyl (diphenyl) pyrrolopyrrole (DPP of formula IIa in which G ₂ = para-chlorophenyl and G. = para-tert-butylphenyl [G ₂ -G-]);

in Example 17: diketo-4-chloro-4-phenyl (diphenyl) pyrrolopyrrole (DPP of formula IIIa in which G ₂ = para-chlorophenyl and G 1 = para-phenylphenyl [G ₂ GJ);

In Example 18: diketo-3-bromo (diphenyl) pyrrolopyrrole (DPP of Formula IIa in which G ₂ = meta-bromophenyl and G 1 = phenyl [G ₂ * G.]);

in Examples 19 to 21 (preparation of bis-DPP): diketo-4-chloro-4-phenyl (diphenyl) pyrrolopyrrole (DPP of formula IIb wherein G ₂ = para-chlorophenyl and G ₁ = phenyl), wherein in Examples 22 to 28 The procedure is the same as in Example 1 except that instead of Example 1, DPP of Formula XXII is used: Example 22: (a composition comprising halo-DPP of Formula XXII and DPP of Formula IIa in which G ₂ = G, = para -Cl-phenyl) thiol in stoichiometric amount relative to halo-DPP of formula XXII, and in Example 23: 1,3-dimethyl-3,4,5,6-tetrahydro-3 (1H) pyrimidinone was used in place of DMA and in Examples 24 to 28: different bases are used.

• · • ·

Table 1: Examples 1-28, analogous to Example 1, wherein the starting materials, reaction parameters and yields are shown in the table.

Example 'Amount DPP (G) Thiol Amount thiol dissolved in v rozp.faú) deity solvent- bodies (ml) Base deity base (G) Reaction time/ temperature (h) / (K) 1 10.72 1-cktadďan- hibhibL 17.19 g v 60 ml DMA 260 ml DMA K ₂ CO ₃ 9.95 24/393 2 10.72 2-frerkapto- etřand 4.21 ml _in 40 ml DMA 260 ml DMA K2CO3 9.95 2/393 3 10.72 1-Nannanhide. 9.62 ml _in 40 ml DMA 260 ml DMA K2CO3 9.95 4.5 / 403 4 10.72 ethylthio- gfykdLát 7.24 g v 40 ml DMSO 260 ml “DMSO K ₂ CO ₃ 9.95 19/371 5 10.72 p-methylthic fend 7.45 g v 40 ml DMA 260 ml DMA K2CO3 9.95 18.5 / 383 6 10.72 4-nerkapto- ferbL 9-25 g h 40 ml DMA 260 ml DMA K2CO3 9.95 17 / 393- 403 7 10.02 1-prcpart- hibhibL 6.39 g v 30 ml DMA 230 ml DMA K2CO3 9.28 19.5 / 403 8 10.72 1-doddan- thibL 15.18g _in 50 ml DMA 350 ml DMA K2CO3 10.36 16/393 9 5.36 2-dineth / l- amiroetřan- Ihici 6.37 g v 40 ml “DMSO 130 ml “DMSO K ₂ CO ₃ 4.98 22.5 / 383 10 5.36 1-tejsn- thioL 3.55 g h 40 ml DMA 170 ml DMA K2CO3 4.98 18.3 / 393 11 5.35 1-cktačit- canthiol 10.32 g _in 20 ml DMA 130 ml DMA K2CO3 4.98 6.25 / 413 12 2.34 1-rrrHn- thiol 5.29 v 10 ml DMA 70 ml DMA K ₂ CO ₃ 1.82 18.5 / 393

• ·

Table 1 (continued)

Example Thickness DPP (G) Thiol divinity thiol dissolved in v rozp.feú) dnožství solvent- bodies (ml) Base deity base (G) Reaction time/ temperature (h) / (K) 13 2.34 1-rcranthki 5.29 v 10 ml DMSO 80 ml DMSO K ₂ CO ₃ 1.82 18.5 / 393 14 9.04 2-diiretyl- arinoethane- thid 8.35 g v 30 ml DMSO 250 ml DMSO K ₂ CO ₃ 1.82 20/373 15 Dec 10.1 2-diinsyl ariností-Brt- thibL 8.35 g v 30 ml DMSO 250 ml DMSO K ₂ CO ₃ 1.82 20/373 16 5.68 2-dirreth / L- amrcetban- thibL 8.35 g v 30 ml DMSO 250 ml DMSO K ₂ CO ₃ 1.82 20/373 17 9.97 ž-čtínetíyl- amirEethyn- thiol 8.35 g v 30 ml DMSO 250 ml DMSO K ₂ CO ₃ 1.82 20/373 18 4.04 1-cktadé <an thiol 6.3 g h 10 ml DMA 130 ml DMA. K ₂ CO ₃ 3.65 6/403 19 Dec 4.84 1,3-pxpsn- diťhibL 1.62 g 100 ml DMA K ₂ CO ₃ 2.9 6/380 20 May 4.84 1,5-ps ± an- dithibL 2.04 g 100 ml DMA K ₂ CO ₃ 2.9 6/380 21 4.84 1,5-te> heart- ťhici 1.41 g 100 ml DMA K ₂ CO ₃ 2.9 6/380 22nd 5.36 2-dinethyl- amiroet ± an- hibhibl 1.06 g 20 ml DMSO 130 ml DMSO K ₂ CO ₃ 2.07 0.5 / 354 23 10.72 1-ckfcads- kanthidL 17.19 g in 60 ml ^A 260 ml ^A K ₂ CO ₃ 9.95 24/393

Table 1 (continued)

Example Amount DPP (G) Thiol Amount thiol dissolved in v rozp.fcnl Amount solvent- bodies (ml) Base Amount base (G) Reaction time/ temperature (h) / (K) 24 10.72 1-cktaddsn- ťhioL 17.19 g v 60 ml 260 ml N32CO3 9.95 24/393 25 10.72 1-ckfca ^ an- thidL 17.19 g v 60 ml 260 ml KHCO3 9.95 24/393 26 10.72 l-cktvrbten- thidL 17.19 g v 60 ml 260 ml On 9.95 24/393 27 Mar: 10.72 l-ckfcaddan- ± idl 17.19 g v 60 ml 260 ml KOH 9.95 24/393 28 10.72 l-cktaddon- ťhici 17.19 g v 60 ml 260 ml NaOH 9.95 24/393

**) DMSO is dimethylsulfoxide

λ) 1,3-dimethyl-3,4,5,6-tetrahydro-3 (1 H) pyrimidinone

Table 2: Examples 1 to 28, wherein the treatment and isolation is carried out analogously to Example 1

Example Amount of water / · OnL) Methanol CmL) Water Drying temperature (K) Yield (g /%) theory, mass) 1 600 + + 353 24.37g / 94.7% 2 600 300 * + 353 12.21g / 92.4% 3 600 (1.5 1) 353 16.83 g / 92.7% 4 600 *** + + 343 12.65 g / 80.4% '

Table 2 (continued)

Example 1 dnožství leixé-vcdy (ni) Methanol (ni) Water 1 Temperature " IBation (K) Yield (g /% trippy, wt.) 5 600 + Italy (11) 343 14.96 g / 93.4% 6 600 (150 ml) 343 15.17 g / 94.2% 7 500 (1.5 I) (1.5 I) 343 9.98 g / 81.4% 8 700 d (i) (0.8 I) 353 19 g / 92.1% 9 300 (1 i) (0.5 I) 343 7.12 g / 96.0% 10 300 (1 O (0.5 I) 343 7.11 g / 91.0% 11 300 (1.5 I) ” (1 i) ···· 343 8.5 g / 82.6% .12 200 (0.51) 343 1.82 g / 49.1% 13 200 (0.5I) 343 2.41 g / 65.0% 14 500 + (1.51) + (1 O 343 10.6 g / 96.7% 15 Dec 500 + (1.5 I) + (1 i) 343 11.88 g / 97.65% 16 500 (1-5 I) (1 O 343 6.6 g / 98% 17 500 (1-5 I) (1 O 343 10.76 g / 92% 18 300 (1.5 I) (0.75 I) 343 5.74 g / 91.1% 19 Dec 200 (0.5 I) (0.2 I) 343 4.53 g / 88.7%

Example Quantity Jfiábué vxiy (ml) MethanoJ (ml) Water Temperature SLffiní (K) / Yield (g /% theory) 20 May 200 (0.5 I) (0.2 I) 343 5.22 g / 98.2% 21 200 (0.5 l) (0.2 I) 343 5.27 g / 97.2% 22nd 300 (0.5 l) 343 4.97 g 23 600 + + 353 94% 24 600 + + 353 99% 25 600 + + 353 95% 26 600 + + 353 96% 27 Mar: 600 + + 353 98% 28 600 + + 353 99%

+ means: means:

component is used in the reaction component is not used in the reaction * Example 2: the filter residue is taken up in 300 ml of methanol and the resulting mixture is stirred at room temperature (T 295 K) for 12 hours; the methanolic reaction mixture is filtered and the residue on the filter is washed with water.

*** Example 4: The reaction mixture is poured into 600 ml of ice water and neutralized with hydrochloric acid to pH 7; the aqueous reaction mixture was filtered and the filter residue was washed with methanol and water.

**** Example 11: after washing the filter residue with methanol and then water, the residue is mixed with ethyl acetate and the resulting mixture is heated to boiling and stirred for 2 hours; the reaction mixture is then filtered and the residue is dried under vacuum at 343 K.

***** Examples 12 and 13: after washing the filter residue with water, this residue is mixed with ethyl acetate, and the mixture is heated to boiling under stirring for 6 hours; the reaction mixture is then filtered and the filter residue is dried under vacuum at 343 K.

****** Examples 19 to 21: proceed as in ***** except that DMA is used instead of ethyl acetate.

******* Example 22: after washing the residue on the filter with water, it is mixed with 300 ml of a 1: 1 by volume mixture of ethanol and water and the resulting mixture is stirred at room temperature; the reaction mixture is then filtered and the filter residue is washed with 300 ml of methanol and then with 300 ml of water and dried under vacuum at 343 K.

9 • 9

Table 3: Elemental analyzes of the products of Examples 1 to 21

Analysis C H N Cl WITH Example 1 calculated 75.65% 9.87% 3.27% 7.48% found 75.61% 9.67% 3.38% 7.46% Example 2 calculated 59.98% 4.58% 6.36% 14.56% found 59.67% 4.66% 6.25% 14.66% Example 3 calculated 71.48% 8.00% 4.63% 10.60% found 71.40% 8.10% 4.38% 10.46% Example 4 calculated 59.53% 4.61% 5.34% 12.22% found 59.74% 4.16% 6.05% 12.22% Example 5 calculated 72.16% 4.54% 5.26% 12.04% found 72.25% 4.54% 5.25% 11.96% Example 6 calculated 67.15% 3.76% 5.22% 11.95% found 65.73% 4.19% 5.52% 11.24% Example 7 calculated 66.03% 5.54% 6.42% 14.69% found 66.17% 5.43% 6.66% 14.75% Example 8 calculated 73.21% 8.87% 4.07% 9.31% found 73.08% 8.49% 4,11% 9.28% Example 9 calculated 63.13% 6.11% 11.33% 12.96% found 63.17% 6.13% 10.73% 13.03% Example 10 calculated 69.19% 6.97% 5.38% 12.31% found 69.96% 6.88% 5.64% 11.49% Example 11 calculated 75.65% 9.87% 3.27% 7.48% found 75.63% 9.84% 3.36% 7.30% Example 12 calculated 64.17% 6.88% 4.16% 10.52% 9.52% found 63.66% 6.83% 4.35% 10.68% 9.07% Example 13 calculated found 69.19% 69.96% 6.97% 6.88% 5.38% 5.64% 12.31% 11.49% Example 14 calculated found 69.19% 69.96% 6.97% 6.88% 5.38% 5.64% 12.31% 11.49%

• · · fc · ·

Table 3 (continued)

Analysis C H N Cl WITH Example 15 calculated found 69.19% 69.96% 6.97% 6.88% 5.38% 5.64% 12.31% 11.49% Example 16 calculated found 69.19% 69.96% 6.97% 6.88% 5.38% 5.64% 12.31% 11.49% Example 17 calculated found 69.19% 69.96% 6.97% 6.88% 5.38% 5.64% 12.31% 11.49% Example 18 calculated found 69.19% 69.96% 6.97% 6.88% 5.38% 5.64% 12.31% 11.49% Example 19 calculated found 68.81% 68.82% 4.15% 3.99% 8.23% 8.37% 9.42% 9.56% Example 20 calculated found 69.47% 69.32% 4.55% 4.71% 7.9% 7.86% 9.05% 9.52% Example 21 calculated found 69.79% 69.32% 4.74% 4.63% 7.75% 7.67% 8.87% 9.43%

Table 4: List of compounds of Examples 1 to 28

17 17 C C / ' ⁵ HN Q NH ° w ^R w R.. Examples l \ _ω ι I -1 2 Examples R 1t, R 1 = -S- (CH ₂ ) ₁₇ CH ₃ R 19, R 25 = H 1, 23-28 and 22 (Example 22: Halo- DPP) G ₇ = propylene 19 Dec R 17, R 8 = -S- (CH _{2) 2} -OH R191 Rasmussen H 2 G ₇ = pentylene 20 May R, 7. R t = -S- (CH ₂ ) ₈ CH ₃ R 19. R2S- = H 3 G ₇ = hexylene 21 R 17> R 16 ⁼ -S-CH ₂ -COOCH ₂ ch ₃ R 19. Ras = H 4 - · R17, Rte = -S- phenyl- (paramethyl) R, 9. Ras = H 5 R17. Rte = -S- phenyl- (parahydroxy) R19. R2S-H 6 R, 7. R t = -S- (CH ₂ ) ₂ CH ₃ R 19. Ras - H 7 R, 7. R, e = -S- (CH ₂ ) n CH ₃

Table 4 (continued)

% R HN jC NH ⁰ p ^ 25 R ^π 18 Examples R 11, R 11 = -S- (CH ₂ ) ₂ N (CH ₃ ) ₂ R ₁₉ , R _{2 S} = H 9 R 11, R 16 = -S- (CH ₂ ) ₅ CH ₃ R 19, R 25 = H 10 R 17, R 18 = -S- (CH ₂ ) ₁₇ CH ₃ R 18, R 25 = H 11 Rn. R ₁₈ = -S- (CH ₂ ) ₈ CH ₃ R ₁₉ , R 25 ⁼ Cl 12, 13 R 17 = -S- (CH ₂ ) ₂ N (CH ₃ ) ₂ R 19, R 25, R 16 = H 14 R, ₇ = -S- (CH ₂ ) ₂ N (CH ₃ ) ₂ R 19, R 25 = H R 18 ⁼ CH ₃ 15 Dec R 17 = -S- (CH ₂ ) ₂ N (CH ₃ ) ₂ R 19, R 25 = H R ₁₈ = -C (CH ₃ ) ₃ 16 R 7 = -S- (CH _{2) 2} N (CH _{3) 2} R, 9th R 25 = H R 16 = phenyl 17 R ₉ = -S- (CH _{2) 7} CH ₃ Rl7. R25. R18 = H 18

PATENTOVÉ Claims 1. Method of preparation alkylthio- and / or

Claims (12)

PATENTOVÉ Claims 1. Method of preparation alkylthio- and / or an arylthio-substituted diketodiarylpyrrolopyrrole (DPP) of formula (Ia) or a bis-diketodiarylpyrrolopyrrole with a dithio-bridge group (bis-DPP) of formula (Ib) wherein in formula (Ia) G represents a phenyl group substituted with at least one arylthio or alkylthio group and G. represents G or a carbocyclic or heterocyclic group and in the general formula Ib G, represents a phenylene group, G _t is G but not G a G ₇ is an alkylene, cycloalkylene or phenylene group, by reacting a haloaryl with a thiol or a thiolate to prepare a compound of formula (Ia) and by reacting two haloaryl with a dithiol or a dithiolate to prepare a compound of formula (Ib); a thiol or thiolate with a halo-di-diarylpyrrolopyrrole of formula IIa (halo-DPP) of the general formula wherein G ₂ is a halogenated phenyl group and G ₃ is G ₂ or G 1, or is reacted with di-thiol or dithiolate with two halo-di-diarylpyrrolopyrroles Hal in which Hal represents a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The process according to claim 1, wherein the thiol or thiolate used is a compound of formula IIIa or a dithiol or dithiolate of formula IIIb. R _r SR ₂ lila, RS-G ₇ -SR ₂ Illb in which R. represents an alkyl group containing 1 to 30 carbon atoms which may be uninterrupted or interrupted once or several times by heteroatoms such as -O- or -S-, or -NH-, -C (O) O-, -OC ( O) - or -C (O) -NH-, a. Which may be substituted or unsubstituted, or a C 5 -C 12 cycloalkyl group or a phenyl group, which may be substituted or unsubstituted, R. represents a hydrogen atom, an alkali metal cation (M) or a nitrogenous organic base, and G- represents an alkylene group having 1 to 30 carbon atoms, which may be uninterrupted or interrupted once or several times by heteroatoms such as -O- or -S-, or -NH-, -C (O) O-, -OC ( O) - or -C (O) -NH-, and which may be substituted or unsubstituted, a cycloalkylene group containing atoms or a phenylene group, substituted or unsubstituted. 5 to 12 carbon which they can be 3. The method of claim 2 č e n ý t í m that alkyl group substituents, cycloa 1kýlové groups or phenyl groups are alkyl groups containing 1 to 18 carbon atoms, OR., SR-, C (O) R, COOR ₃ , -OCOR ₅ , SO ₃ R ₃ , SO ₂ R ₃ , PO ₃ R ₃ , Si (OR)., Salt group SM, OM, COOM, SO.M, PO ₃ M, P (R) / X ', P ((R ₃ ) ₂ R) ₁₃ dC, NO ₂ , N (R) f X ', N ((R ₃ ) ₂ R ₄ ) / X or a nitrogen-containing group, wherein in said substituent groups R 1 and R 3 are independently hydrogen, C 1 -C 18 alkyl, C 5 -C 6 cycloalkyl or unsubstituted or R ₇ -substituted phenyl, M represents an alkali metal cation, preferably sodium or potassium, X 'represents a halide anion such as fluoride, a chloride, bromide or iodide anion, and R ₇ is H, a hydrogen atom, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group containing 1 to 8 carbon atoms or unsubstituted or NR, R ₄ substituted cycloalkyl having 5 or 6 carbon atoms. 4. The method of claim 1, wherein G ₂ in halogendiketodiarylpyrrolopyrrolu formula IIa is an unsubstituted or substituted, halogenated phenyl group and G is G ₂ or G ,, _G or halogendiketodiarylpyrrolopyrrolu the formula IIb is G ,, wherein G represents a heterocyclic group or a carbocyclic group of the formulas XI, XII, XIII in which R., R. _a , R, _o and R ,. independently of one another are hydrogen, halogen, such as fluorine, chlorine, bromine or iodine, an alkyl group containing 1 to 18 carbon atoms, an -E-alkyl group in which the alkyl moiety contains 1 to 18 carbon atoms , -CN, -NO., trifluoromethyl, cycloalkyl having 5 or 6 carbon atoms, or -C = N • wherein E represents -O-, -S-, -NH-, -C (O) O-, -OC (O) -, - (CO) NH-, -NHC (O) -, and R., represents a single bond, -CR-, -CH (CH 2) -, -C (CH 2) -, - CH = N-, -O-, -S-, -SO-, -SCX- or -NR 3 -. The process according to claim 1 or 4, wherein G ₂ is a group Hal y y n of formula XV XV in which Hal represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom and R @ 1 and R @ 2 independently of one another are, for example, hydrogen, CN, CE, C1 -C5 alkyl, C5 -C6 cycloalkyl, -E-alkyl in which the alkyl moiety contains 1 to 5 carbon atoms; up to 18 carbon atoms, phenyl, SR, amide groups such as -COR, R ₄ , or amide groups of formulas XVI to XIX XVIII XIX or amide groups of nitrogen-containing heterocycles such as 1-carbonylimidazole, 1-carbonylpyrazole, 1-carbonyltriazole, 1-carbonylpyrrole, 1-carbonylpyrrolidine, 1-carbonylbenzimidazole or A 1-carbonylbenzotriazole group, or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Process according to any one of claims 1 to 5, characterized in that it is carried out in the presence of a base. A process according to any one of claims 1 to 6, characterized in that it is carried out in the presence of a solvent. 8. Alkylthio- and / or arylthio-substituted diketodiarylpyrrolopyrrole (DPP) of formula XXI or XXX XXI or a bis-diketodiarylpyrrolopyrrole of formula Ib [0057] Ib. wherein said general formulas R, R, R, R _,. and R _2, independently of one another are hydrogen, R_, and R ₄ represents karbocyklickou- or heterocyclic group with the proviso that a) R, in formula XXI is not phenyl when R ₅ and R , _t is hydrogen and G. is phenyl, and that b) R, in formula XXX, is not a phenylenalkyl group in which the alkyl radical is 1 to 4 carbon atoms when R 1, R ₂ , R ₂ , . and _R21 is hydrogen, G _{= a} phenylene group, G 1 represents a carbocyclic or heterocyclic group and G- represents an alkylene group, a cycloalkylene group or a phenylene group. A composition comprising a diketodiarylpyrrolopyrrole of formula XXI and / or XXX according to claim 8 and a diketodiarylpyrrolopyrrole of formula Ia and / or Ib and a diketodiarylpyrrolopyrrole or diketodiarylpyrrolopyrrole latent pigment, wherein the diketodiarylpyrrolopyrrole of formula XXa and Ib are XX and XXa. A composition comprising a diketodiarylpyrrolopyrrole of formula XXI or XXX or a bis-diketodiarylpyrrolopyrrole of formula Ib according to claim 8 and a high molecular weight organic substance. Use of a diketodiarylpyrrolopyrrole of formula Ia or a bis-diketodiarylpyrrolopyrrole of formula Ib, prepared according to claim 1, as a rheology improving agent. Use of a diketodiarylpyrrolopyrrole of the formula Ia or a bis-diketodiarylpyrrolopyrrole of the formula Ib, prepared according to claim 1, as an inhibitor of crystal growth. Use of a diketodiarylpyrrolopyrrole of formula XXI or XXX or a bis-diketodiarylpyrrolopyrrole of formula Ib according to claim 8 or a composition according to claim 9 for coloring / pigmenting a high molecular weight organic substance.