DE102007039155A1 - Catalytically preparing aromatic or heteroaromatic aryl amine, preferably N-monoalkyl aryl- or heteroaryl-amine, comprises reacting aliphatic amine with aryl amine in the presence of ruthenium-, iridium- or rhodium-compound as catalyst - Google Patents

Abstract

Catalytically preparing aromatic or heteroaromatic aryl amine (I), comprises reacting an aliphatic amine (IX) with an aryl amine (VIII) in the presence of ruthenium-, iridium- or rhodium-compound as catalyst. Catalytically preparing aromatic or heteroaromatic aryl amine of formula (Ar1-NH-R) (I), comprises reacting an aliphatic amine of formula (R 1>) n-N-(R 2>) m(IX) with an aryl amine of formula (Ar1-NH 2) (VIII) in the presence of ruthenium-, iridium- or rhodium-compound as catalyst. Ar1 : aromatic- or heteroaromatic-residue (both optionally substituted); R, R 1>aliphatic residue; R 2>H or aliphatic residue; n : 1-3; and m : 0-2.

Description

The The present invention relates to a method for selective production of N-monoalkylated aromatic or heteroaromatic arylamines by reaction of aryl or heteroarylamines with aliphatic Amines. It can be primary, secondary and tertiary aliphatic amines are used. It will each aliphatic radical is transferred to exactly one aryl amine.

Aromatic and heteroaromatic arylamines have industrial significance as starting materials for fine chemicals, agro products and intermediates for the pharmaceutical industry. Therefore, processes for their production are of industrial importance. A well-known and industrially applied method for the preparation of N-substituted aromatic amines is the reaction of aryl halides, aryl tosylates and aryl triflates with aliphatic amines (Buchwald: WO 2003066570 . WO 2004013094 . WO 2000005199 ; Hartwig: US 6235938 . US 6100398 . US 5977361 ). However, this method is only practical if the corresponding starting materials (aryl halides, aryl tosylates and aryl triflates) are available at low cost. In addition, one or more equivalents of a base must be used, which is converted to one equivalent of salt. Furthermore, reactions with primary aliphatic amines, and thus the production of monoalkylated arylamines, as well as the reactions of pyridine derivatives are problematic.

Another method for the preparation of monoalkylated aromatic amines is the reaction of anilines with alcohols. Thus, Y. Takebayashi, T. Sugeta, S. Yoda, K. Otake, Y. Marito, H. Sakei, M. Abe ( JP 2006028145 ) the reaction of aniline in the presence of primary alcohols using alkali catalysts. A review of reactions of alcohols with arylamines and amines has recently been reported by Williams et al. ( Adv. Synth. Catal. 2007, 349, 1555 ) released.

Furthermore, anilines can also be prepared by an aza-Wittig reaction. It sat Williams at al. (Chem. Commun. 2004, 1072 ) Iminophosphoranes with aldehydes in the presence of a Iridiumkartalysators to.

Another production method of anilines is the reaction of ammonia and amines with phenols. Drastic conditions (450 ° C or 510 ° C) and heterogeneous catalysts are necessary (ammonia: JP 07070001 . JP 07215919 ; Amine: EP 62542 ). However, such processes are disadvantageous because of the drastic reaction conditions and generally can not be applied to more complex substituted aromatic amines.

In summary It should be noted that previous known transition metal catalyzed Alkylations either alcohols, aryl halides or the like Use substrates and / or substance mixtures of mono- and dialkylated Arylamines arise.

task The present invention was the development of a new highly selective A method for the N-monoalkylation of arylamines, in particular to This method can be used well on an industrial scale and be cost effective.

The stated object has been achieved by a catalytic preparation of N-monoalkylated aromatic or heteroaromatic arylamines of the general formula (I) Ar-NH-R (I) by reacting corresponding aliphatic amines of the general formula IX (R ¹ ) _n -N- (R ² ) _m (IX) with an arylamine of the general formula (VIII) Ar-NH ₂ (VIII) in the presence of ruthenium, iridium or rhodium compounds as catalysts, wherein
Ar is an aromatic or heteroaromatic radical which is optionally substituted,
R is any aliphatic radical R ¹ or any desired aliphatic radical R ² ,
R ^{1 represents} any aliphatic radical,
R ² signifies H or any aliphatic radical identical or different from R ¹ ,
n = 1, 2 or 3 and
m = 0, 1 or 2.

According to general formula (IX), the aliphatic amines have the preferred structures (II) to (VII) and can be used individually or in mixtures with one another according to the invention: R ¹ -NH ₂ (II) (R ¹ ) ₂ -NH (III) R ¹ -NH-R ² (IV) (R ¹ ) ₃ -N (V) (R ¹ ) ₂ -NR ² (VI) and / or R ^{1 is} -N- (R ² ) ₂ (VII).

When Ruthenium compounds can be any ruthenium salts or Ruthenium complexes, in particular Shvo or Shvo-type complexes used become. Preference is given to ruthenium complexes with cyclopendadienone ligands, such as Shvo's diruthenium hydride complex [1-hydroxytetraphenylcyclopentadienyl (tetraphenyl-2,4-cyclopentadien-1-one) -μ-hydrotetracarbonyl-dinuthenium], Shvo's (Cyclopendadienone) ruthenium dimer, [(tetraphenyl-2,4-cyclopentadien-1-one) -triphenylphosphine tetracarbonyl-dinuthenium)], [(Tetraphenyl-2,4-cyclopentadiene-1-one) -tricyclohexylphosphin-tetracarbonyldiruthenium)], [(Tetraphenyl-2,4-cyclopentadiene-1-one) -n-hexylamintetracarbonyldiruthenium)],

When Rhodium compounds can be any rhodium salts or Rhodium complexes, in particular with cyclopentadienyl ligands, such as for example, dicarbonyl (pentamethylcyclopentadienyl) rhodium (I), Dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, acetonitrile bis [2-diphenylphosphino-6-t-butylpyridine] cyclopentadienylruthenium (II) hexafluorophosphate, bis (cyclopentadienyl) ruthenium, bis (ethylcyclopentadienyl) ruthenium (II), bis (pentamethylcyclopentadienyl) ruthenium, chloro (1,5-cyclooctadiene) (pentamethylcyclopentadienyl) ruthenium (II), chloro (cyclopentadienyl) [bis (diphenylphosphino) methane] ruthenium (II), chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium, dichloro (pentamethylcyclopentadienyl) ruthenium (III).

When Iridium compounds may be any iridium salts or Iridium complexes, in particular with cyclopentadienyl ligands such as Example dichloro (pentamethylcyclopentadienyl) iridium (III) dimer and (methylcyclopentadienyl) (1,5-cyclooctadiene) iridium (I) become.

The used ruthenium, iridium or rhodium compounds preferably used in a sufficient amount in the reaction mixture. The person skilled in the art will use the necessary amount on the basis of economic considerations (Rate of reaction, yield, material costs) select. With the method according to the invention can Turnover values of the catalysts in the order of magnitude from at least 50 to> 100,000 will be realized. Particularly preferred is the use of ruthenium, Iridium or rhodium compound in an amount of 100 ppm to 10 mol% based on the alkylamine or mixture used.

When Solvents find in the inventive Processes generally inert organic solvents and / or Water use. Particularly advantageous are polar protic solvents such. B. tertiary alcohols, polar aprotic solvents such. B. DMSO and nonpolar Solvents such. As heptane, toluene and mixtures thereof proved. Particularly advantageous is the use of t-amyl alcohol. The reactions can also be carried out in bulk become.

The Reaction is preferred at temperatures of 20 to 220 ° C. carried out. In particular, at reaction temperatures from 80 to 200 ° C, more preferably at 100 to 180 ° C, worked.

The Reaction is preferably carried out without pressure. she can but also without problems under pressure, z. B. in an autoclave or pressure tube, are performed.

Optionally, reaction-accelerating or catalyst-stabilizing additives are added. This purpose is fulfilled, for example, by neutral, anionic or cationic ligands which bind to the ruthenium, iridium or rhodium catalyst. Such ligands are inorganic (eg, phosphines, phosphites) and organic ligands (eg, amines). In general, the ligand is used in a ratio of 100: 1 to 1:10 to the ruthenium, iridium or rhodium complex. Optionally, addition of several ligands leads to synergistic positive effects.

In principle, there is no restriction with regard to the use of aromatics or heteroaromatics. In particular, the radical Ar may be a (C ₅ -C ₁₉ ) -aryl radical or a (C ₃ -C ₁₈ ) -heteroaryl radical.

By a (C ₅ -C ₁₉ ) -aryl radical is meant an aromatic radical having 6 to 18 C atoms. In particular, these include compounds such as phenyl, naphthyl, anthryl, phenanthryl, biphenyl. This may be mono- or polysubstituted with (C ₁ -C ₈ ) -alkoxy, (C ₁ -C ₈ ) -haloalkyl, OH, halogen, NH ₂ , NO ₂ , SH, S- (C ₁ -C ₈ ) -alkyl, (C ₁ -C ₈ ) acyl, (C ₁ -C ₈ ) alkyl substituted.

A (C ₃ -C ₁₈ ) heteroaryl radical in the context of the invention denotes a five-, six- or seven-membered aromatic ring system of 3 to 18 C atoms which has 1, 2 or 3 heteroatoms, preferably nitrogen, oxygen or sulfur in the ring. As such heteroaromatics especially radicals are considered such. 1-, 2-, 3-furyl, 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-pyridyl, 2-, 3-, 4- , 5-, 6-, 7-indolyl, 3-, 4-, 5-pyrazolyl, 2-, 4-, 5-imidazolyl, acridinyl, quinolinyl, phenanthridinyl, 2-, 4-, 5-, 6-pyrimidinyl.

It is possible that the radical Ar may carry substituents which are independently (C ₁ -C ₈ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl, (C ₂ -C ₈ ) -alkenyl, (C ₂ - C ₈ ) -alkynyl, (C ₇ -C ₂₀ ) -aralkyl radical, OH, O - [(C ₁ -C ₈ ) -alkyl], OC (O) - [(C ₁ -C ₈ ) -alkyl], O Phenyl, phenyl, NH ₂ , NO ₂ , NO, N [(C ₁ -C ₈ ) alkyl] ₂ , NH [(C ₁ -C ₈ ) alkyl], C (O) NH - [(C ₁ -C ₈ ) -alkyl], C (O) N [(C ₁ -C ₈ ) -alkyl] ₂ , N [(C ₁ -C ₈ ) -alkyl] C (O) - [(C ₁ -C ₈ ) -Alkyl], SH, S-phenyl, S - [(C ₁ -C ₈ ) -alkyl], iodine, bromine, fluorine, chlorine, CF ₃ , CN, COOH, COO - [(C ₁ -C ₈ ) Alkyl], COO-phenyl, CONH-phenyl, OHO, SO ₂ - (C ₁ -C ₈ ) -alkyl, SO- (C ₁ -C ₈ ) -alkyl, PO- (phenyl) ₂ , PO - [( C ₁ -C ₈ ) -alkyl] ₂ , PO ₃ H ₂ , PO [O- (C ₁ -C ₈ ) -alkyl] ₂ , SO ₃ H, SO ₃ M, SO ₃ - [(C ₁ -C ₈ ) Alkyl], Si [(C ₁ -C ₈ ) alkyl] ₃ , (C ₁ -C ₈ ) haloalkyl and (C ₁ -C ₈ ) acyl.

in principle exists with regard to the use of aliphatic amines of general formula IX also no limitation.

In the process according to the invention, preference is given in particular to using the compounds II-VII individually or in a mixture II and / or III and / or IV and / or V and / or VI and / or VII, in which R ¹ and R ^{2 are} independently (C ₁ -) C ₈ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl, (C ₂ -C ₈ ) -alkenyl, (C ₂ -C ₈ ) -alkynyl, (C ₇ -C ₂₀ ) -aralkyl radical and (C ₄ - C ₁₉ ) heteroaralkyl.

It is possible that the above-described radicals (C ₁ -C ₈ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl, (C ₂ -C ₈ ) -alkenyl, (C ₂ -C ₈ ) -alkynyl, ( C ₇ -C ₂₀ ) -Aralkylrest can carry substituents independently of each other (C ₁ -C ₈ ) alkyl, (C ₃ -C ₈ ) -cycloalkyl, (C ₂ -C ₈ ) alkenyl, (C ₂ -C ₈ ) -alkynyl, (C ₇ -C ₂₀ ) -aralkyl radical, OH, O - [(C ₁ -C ₈ ) -alkyl], OC (O) - [(C ₁ -C ₈ ) -alkyl], O- Phenyl, phenyl, NH ₂ , NO ₂ , NO, N [(C ₁ -C ₈ ) -alkyl] ₂ , NH [(C ₁ -C ₈ ) -alkyl], C (O) NH - [(C ₁ - C ₈ ) -alkyl], C (O) N [(C ₁ -C ₈ ) -alkyl] ₂ , N [(C ₁ -C ₈ ) -alkyl] C (O) - [(C ₁ -C ₈ ) Alkyl], SH, S-phenyl, S - [(C ₁ -C ₈ ) -alkyl], iodine, bromine, fluorine, chlorine, CF ₃ , CN, COOH, COO - [(C ₁ -C ₈ ) - Alkyl], COO-phenyl, CONH-phenyl, CHO, SO ₂ - (C ₁ -C ₈ ) -alkyl, SO- (C ₁ -C ₈ ) -alkyl, PO- (phenyl) ₂ , PO - [(C ₁ -C ₈ ) -alkyl] ₂ , PO ₃ H ₂ , PO [O- (C ₁ -C ₈ ) -alkyl] ₂ , SO ₃ H, SO ₃ M, SO ₃ - [(C ₁ -C ₈ ) -Alkyl], Si [(C ₁ -C ₈ ) -alkyl] ₃ , (C ₁ -C ₈ ) -haloalkyl, and (C ₁ -C ₈ ) -acyl.

As (C ₁ -C ₈ ) -alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl including all binding isomers. These may be mono- or polysubstituted by (C ₁ -C ₈ ) -alkoxy, (C ₁ -C ₈ ) -haloalkyl, OH, halogen, NH ₂ , NO ₂ , SH, S- (C ₁ -C ₈ ) -alkyl be.

By (C ₃ -C ₈ ) -cycloalkyl is meant cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl radicals, etc. These may be substituted by one or more halogens and / or N, O, P, S atom-containing radicals and / or have N, O, P, S atoms in the ring, e.g. 1-, 2-, 3-, 4-piperidyl, 1-, 2-, 3-pyrrolidinyl, 2-, 3-tetrahydrofuryl, 2-, 3-, 4-morpholinyl. This may be mono- or polysubstituted with (C ₁ -C ₈ ) -alkoxy, (C ₁ -C ₈ ) -haloalkyl, OH, halogen, NH ₂ , NO ₂ , SH, S- (C ₁ -C ₈ ) -alkyl, (C ₁ -C ₈ ) acyl, (C ₁ -C ₈ ) alkyl substituted.

As (C ₂ -C ₈ ) -alkenyl, with the exception of methyl, it is meant a (C ₁ -C ₈ ) -alkyl radical as shown above which has at least one double bond.

By (C ₂ -C ₈ ) -alkynyl, with the exception of methyl, is meant a (C ₁ -C ₈ ) -alkyl radical as shown above which has at least one triple bond.

A (C ₇ -C ₂₀ ) -aralkyl radical is a (C ₆ -C ₁₉ ) -aryl radical bonded to the molecule via a (C ₁ -C ₈ ) -alkyl radical.

An O - [(C ₁ -C ₈ ) -alkyl] radical is understood to mean a (C ₁ -C ₈ ) -alkyl radical bonded to the molecule via an oxygen atom.

An OC (O) - [(C ₁ -C ₈ ) -alkyl] radical is understood to mean a (C ₁ -C ₈ ) -alkyl radical bonded to the molecule via an oxocarbonyl group.

By an N [(C ₁ -C ₈ ) -alkyl] ₂ and a NH [(C ₁ -C ₈ ) -alkyl] is meant one or two (C ₁ -C ₈ ) -alkyl bonded to the molecule via an amine group -Rest.

By a C (O) N [(C ₁ -C ₈ ) alkyl] ₂ , and a C (O) NH - [(C ₁ -C ₈ ) alkyl] is meant one or two of an amide group to the molecule bonded (C ₁ -C ₈ ) -alkyl radical.

A COO - [(C ₁ -C ₈ ) -alkyl] radical is understood to mean a (C ₁ -C ₈ ) -alkyl radical bonded to the molecule via an ester group.

Under a S - [(C ₁ -C ₈₎ -alkyl] radical is meant a via a sulfur atom bound to the molecule (C ₁ -C ₈₎ -alkyl radical.

A (C ₁ -C ₈₎ haloalkyl means a with one or more halogen atoms, substituted (C ₁ -C ₈₎ -alkyl radical.

A (C ₁ -C ₈₎ acyl is meant an a-C = O function to the molecule bound (C ₁ -C ₈₎ -alkyl radical.

A (C ₄ -C ₁₉ ) -heteroaralkyl is understood as meaning a heteroaromatic system corresponding to the (C ₇ -C ₂₀ ) -aralkyl radical.

When Halogens are fluorine, chlorine, bromine and iodine in question.

The Alkylation of aryl derivatives with aliphatic amines has been reported so far not yet described in the literature. Surprisingly with the method according to the invention N-monoalkylated Arylamines are produced highly selectively. Other advantages are in the wide variety of deployable primary, secondary and tertiary amines (IX) and in the easy accessibility the arylamine (VIII) by a hydrogenation of nitroaromatics. There also mixtures of amines (IX) can be used, amine impurities have no effect on the yield, or even increase it. The only by-product that arises gaseous ammonia, can be separated very well and / or be used elsewhere.

Examples:

General procedure:

In Under argon, the Shvo complex (0.01 equiv.) was added to an ACE pressure tube. and the aliphatic amine (1 equiv.) in t-amyl alcohol (0.5 ml) and aryl or heteroarylamine (2 equiv.). The pressure tube was closed and kept at 150 ° C. for 24 h heated in an oil bath. Sales and yield can over Gas chromatography can be determined. An isolation of the product takes place according to the usual refurbishments (Distillation, crystallization or chromatography).

The following table (Examples 1 to 16) shows N-monoalkylated products using hexylamine:

Examples Figures 17 to 29 show further N-monoalkylated products using various aliphatic amines

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 2003066570 [0002]
• - WO 2004013094 [0002]
• - WO 2000005199 [0002]
• US 6235938 [0002]
• US 6100398 [0002]
• US 5977361 [0002]
• - JP 2006028145 [0003]
• - JP 07070001 [0005]
• - JP 07215919 [0005]
• - EP 62542 [0005]

Cited non-patent literature

• - Adv. Synth. Catal. 2007, 349, 1555 [0003]
• - Williams at al. (Chem. Commun. 2004, 1072 [0004]

Claims (17)

Process for the catalytic preparation of aromatic or heteroaromatic arylamines of the general formula (I) Ar-NH-R (I), characterized in that an aliphatic amine of the general formula (IX) (R ¹ ) _n -N- (R ² ) _m (IX) with an arylamine of the general formula (VIII) Ar-NH ₂ (VIII) in the presence of ruthenium, iridium or rhodium compounds as catalysts, wherein Ar is an aromatic or heteroaromatic radical which is optionally substituted, R is any aliphatic radical R ¹ or any aliphatic radical R ² , R ^{1 is} any is aliphatic radical, R ^{2 is} H or any aliphatic radical is the same or different from R ¹ , n = 1, 2 or 3 and m = 0, 1 or 2. A method according to claim 1, characterized in that as aliphatic amine compounds of the general formulas (II) to (VII) are used, individually or in mixtures with one another R ¹ -NH ₂ (II) (R ¹ ) ₂ -NH (III) R ¹ -NH-R ² (IV) (R ¹ ) ₃ -N (V) (R ¹ ) ₂ -NR ² (VI) and / or R ¹ -N- (R ² ) ₂ (VII) in which R ¹ and R ^{2 have} the abovementioned meaning. Method according to claim 1 or 2, characterized that as ruthenium, iridium or rhodium compounds their salts or complexes are used. Method according to one of claims 1 to 3, characterized in that as ruthenium compounds Shvo or Shvo-type complexes are used, preferably Shvo's diruthenium hydride complex, Shvo's (Cyclopendadienone) ruthenium dimer, [(tetraphenyl-2,4-cyclopentadien-1-one) triphenylphosphine tetracarbonyl-dinuthenium)], [(Tetraphenyl-2,4-cyclopentadiene-1-one) -tricyclohexylphosphin-tetracarbonyldiruthenium)] and [(tetraphenyl-2,4-cyclopentadien-1-one) -n-hexylamine-tetracarbonyl-dinuthenium)]. Method according to one of claims 1 to 4, characterized in that the ruthenium complex in a Amount of 10 ppm to 20 mol% based on the aliphatic used Amine (IX) used. Method according to one of claims 1 to 5, characterized in that the reaction in the presence of catalyst-stabilizing Additives, preferably in the presence of binding to the catalyst neutral, cationic or anionic ligands becomes. Method according to one of claims 1 to 6, characterized in that are used as the catalyst rhodium or iridium with a cyclopentadienyl ligand, preferably dichloro (pentamethylcyclo pentadienyl) rhodium (III) dimer and dichloro (pentamethylcyclopentadienyl) iridium (III) dimer. Method according to one of claims 1 to 6, characterized in that as catalyst-stabilizing additives monodentate or chelating phosphine ligands are used. Method according to one of claims 1 to 8, characterized in that the phosphine ligand in a used in such an amount that the molar ratio of ruthenium, Iridium or rhodium complex to phosphine ligand is 1: 100 to 10: 1. Method according to one of claims 1 to 9, characterized in that the reaction in an inert organic Solvent and / or water takes place. Method according to claim 10, characterized in that that as a solvent protic polar, aprotic polar or nonpolar solvents or mixtures containing two or more of these solvents are used. Method according to one of claims 1 to 11, characterized in that the reaction at temperatures from 20 to 220 ° C, especially at 80 to 200 ° C, particularly preferably at 100 to 180 ° C, takes place. Method according to one of claims 1 to 12, characterized in that the reaction under pressure or without pressure is carried out. Method according to one of claims 1 to 13, characterized in that Ar is a (C ₆ -C ₁₉ ) -aryl radical or a (C ₃ -C ₁₈ ) heteroaryl radical having 1, 2 or 3 heteroatoms, preferably selected from nitrogen, oxygen or Representing sulfur in the ring. A method according to claim 14, characterized in that the radical Ar can carry up to eight substituents independently of one another (C ₁ -C ₈ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl, where the cycle also contains 1-2 heteroatoms selected from the group N and O and the ring size is 3-8, (C ₂ -C ₈ ) alkenyl, (C ₂ -C ₈ ) alkynyl, (C ₇ -C ₂₀ ) aralkyl radical, OH, O - [(C ₁ -C ₈ ) -alkyl], OC (O) - [(C ₁ -C ₈ ) -alkyl], O-phenyl, phenyl, NH ₂ , NO ₂ , NO, N [(C ₁ - C ₈ ) -alkyl] ₂ , NH [(C ₁ -C ₈ ) -alkyl], C (O) NH - [(C ₁ -C ₈ ) -alkyl], C (O) N [(C ₁ -C ₈ ) -alkyl] ₂ , N [(C ₁ -C ₈ ) -alkyl] C (O) - [(C ₁ -C ₈ ) -alkyl], SH, S-phenyl, S - [(C ₁ -C ₈ ) -alkyl], iodine, bromine, fluorine, chlorine, CF ₃ , CN, COOH, COO - [(C ₁ -C ₈ ) -alkyl], COO-phenyl, CONH-phenyl, CHO, SO ₂ - (C C ₁ -C ₈ ) -alkyl, SO- (C ₁ -C ₈ ) -alkyl, PO- (phenyl) ₂ , PO - [(C ₁ -C ₈ ) -alkyl] ₂ , PO ₃ H ₂ , PO [O - (C ₁ -C ₈ ) -alkyl] ₂ , SO ₃ H, SO ₃ M, SO ₃ - [(C ₁ -C ₈ ) -alkyl], Si [(C ₁ -C ₈ ) -alkyl] ₃ , (C ₁ -C ₈ ) haloalkyl and (C ₁ -C ₈ ) acyl Kings be NEN. Method according to one of claims 1 to 15, characterized in that compounds of formula (IX), preferably the compounds II-VII or mixtures of compounds II to VII can be used, wherein R ¹ and R ^{2 are} independently (C ₁ -C ₈ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl, where the cycle may also contain 1-3 heteroatoms selected from the group consisting of N, S and O and the ring size is 3-8, (C ₂ -C ₈ ) - Alkenyl, (C ₂ -C ₈ ) alkynyl, (C ₇ -C ₂₀ ) -Aralkylrest can be. Process according to Claim 16, characterized in that the aliphatic radicals R ¹ and R ² can carry substituents which are independently (C ₁ -C ₈ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl, the cycle also being 1- 2 heteroatoms selected from the group N and O may contain and the ring size is 3-8, (C ₂ -C ₈ ) alkenyl, (C ₂ -C ₈ ) alkynyl, (C ₇ -C ₂₀ ) -Aralkylrest, OH , O - [(C ₁ -C ₈ ) -alkyl], OC (O) - [(C ₁ -C ₈ ) -alkyl], O-phenyl, phenyl, NH ₂ , NO ₂ , NO, N [(C C ₁ -C ₈ ) -alkyl] ₂ , NH [(C ₁ -C ₈ ) -alkyl], C (O) NH - [(C ₁ -C ₈ ) -alkyl], C (O) N [(C ₁ -C ₈₎ alkyl] _2, N [(C ₁ - C ₈₎ -alkyl] C (O) - [(C ₁ -C ₈₎ -alkyl], SH, S-phenyl, S - [(C ₁ -C ₈ ) -alkyl], iodine, bromine, fluorine, chlorine, CF ₃ , CN, COOH, COO - [(C ₁ -C ₈ ) -alkyl], COO-phenyl, CONH-phenyl, CHO, SO ₂ - (C ₁ -C ₈ ) -alkyl, SO- (C ₁ -C ₈ ) -alkyl, PO- (phenyl) ₂ , PO - [(C ₁ -C ₈ ) -alkyl] ₂ , PO ₃ H ₂ , PO [O- (C ₁ -C ₈ ) -alkyl] ₂ , SO ₃ H, SO ₃ M, SO ₃ - [(C ₁ -C ₈ ) -alkyl], Si [(C ₁ -C ₈ ) -alkyl] ₃ , (C ₁ -C ₈ ) -haloalkyl and (C ₁ -C ₈ ) -Acyl can be.