Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B47/00—Porphines; Azaporphines
  • C09B47/04—Phthalocyanines abbreviation: Pc
  • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B47/00—Porphines; Azaporphines
  • C09B47/04—Phthalocyanines abbreviation: Pc
  • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
  • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
  • C09B47/0673—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having alkyl radicals linked directly to the Pc skeleton; having carbocyclic groups linked directly to the skeleton
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B47/00—Porphines; Azaporphines
  • C09B47/04—Phthalocyanines abbreviation: Pc
  • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
  • C09B47/22—Obtaining compounds having nitrogen atoms directly bound to the phthalocyanine skeleton
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/003—Marking, e.g. coloration by addition of pigments
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/28—Organic compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
  • C10M171/007—Coloured or dyes-containing lubricant compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1608—Well defined compounds, e.g. hexane, benzene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/09—Complexes with metals

Definitions

• the present invention relates to a process for the preparation of compounds of
• M 1 , M 2 , M 3 independently of one another, identical or different, Si or Ge,
• E, E ', E independently of one another, identical or different, CH or N, G, G', G" independently of one another, identical or different, CH or N, n, m, p, q independently of one another, identical or different, integers selected from the range of 0 to 2, r integer selected from the range of 1 to (4 + n 2), s integer selected from the range of 1 to (4 + m 2), u whole Number selected from the range of 1 to (4 + p 2), v integer selected from the range of 1 to (4 + q 2),
• W, X, Y, Z independently of one another, identical or different, halogen, nitro, hydroxy, cyano, amino, C 1 -C 20 -alkyl, C 2 -C 2 o-alkenyl, C 2 -C 2 o-alkynyl, Cs ds-cycloalkyl, aryl, heterocycles, C 1 -C 2 O-Al koxy, aryloxy, Ci-C4-dialkylamino, Cs-Ce-cycloalkylamino, CO 2 M, SO 3 M,
• R 1 to R 6 independently of one another, identical or different, Ci-C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 -alkyl kinyl, C 3 -Ci5 cycloalkyl, aryl, arylalkyl, Ci-C 20 -alkoxy, C 1 -C 20 -alkylthio, aryloxy, trialkylsiloxy, CO 2 M, SO 3 M,
• M is hydrogen, alkali metal
• the invention further relates to certain compounds of general formula (I) and to the use of certain compounds of general formula (I) as markers for liquids.
• the invention includes liquids which contain certain compounds of general formula (I) as markers.
• the invention relates to methods for the detection of markers in liquids and for the identification of liquids which contain at least one compound of general formula (I). Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular concretely specified combination but also in other combinations without departing from the scope of the invention. In particular, those embodiments of the present invention in which all features of the article according to the invention have the preferred or very preferred meanings are preferred or very particularly preferred.
• No. 3,509,146 describes the preparation of metal-free phthalocyanines and related compounds from 1,3-diiminoisoindolines or their heterocyclic analogues in conjunction with alkylalkanolamines.
• EP 0 373 643 A2 describes the preparation of metal-containing phthalocyanines from mixtures of o-phthalonitriles and / or 1, 3-diiminoisoindolines by reaction with metallic compounds. This reaction may, according to EP 0 373 643 A2, take place either in the presence of 1, 8-diazabicyclo [5.4.0] -7-undecene (DBU) in alcohols or alternatively in high-boiling solvents such as chloronaphthalene, bromonaphthalene or trichlorobenzene.
• DBU 1, 8-diazabicyclo [5.4.0] -7-undecene
• the metal-containing phthalocyanines of EP 0 373 643 A2 are used as absorbers in the near infrared for optical recording media.
• US 3,094,536 describes the preparation of dichloro and dihydroxy-silicon phthalocyanines. The dichloro-silicon phthalocyanines are prepared from phthalonitriles and silicon
• No. 5,872,248 describes the preparation of silicon phthalocyanines and naphthalocyanines by reaction of the metal-free compounds with trichlorosilane.
• EP 0 499 345 A2 describes the synthesis of dihydroxy-silicon naphthalocyanine and bis (triethylsiloxy) -siliconnaphthalocyanine based on the dichloro compound.
• Dichlorosilicon naphthalocyanine (silicon naphthalocyanine dichloride) is in turn prepared from diiminobenzo (f) -isoindoline with silicon tetrachloride.
• various phthalocyanine and naphthalocyanine derivatives are known as markers for liquids:
• the object of the invention was therefore to find efficient production methods for markers.
• Expressions of the form Ca-Cb in the context of this invention designate chemical compounds or substituents having a certain number of carbon atoms.
• the number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a.
• Further specification of the chemical compounds or substituents is made by expressions of the form Ca-Cb-V.
• V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
• Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
• C 1 -C 20 -alkyl straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, for example C 1 -C 10 -alkyl or C 2 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, for example C 1 -C 3 -alkyl, such as methyl, ethyl, propyl, isopropyl , or C 4 -C 6 -alkyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2,2-dimethylpropyl , 1-ethylpropyl, hexyl, 2- Methylpentyl, 3-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethyl
• C 2 -C 20 -alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and one double bond in any position, for example C 2 -C 10 -alkenyl or C 2 -C 20 -alkenyl, preferably C 2 -C 10 -alkenyl, such as C 2 -C 4 -alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2- propenyl, 2-methyl-2-propenyl, or Cs-C ⁇ -alkenyl, such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-buten
• C 2 -C 20 -alkynyl straight-chain or branched hydrocarbon groups having 2 to 20 carbon atoms and a triple bond in any position, for example C 2 -C 10 -alkynyl or C 2 -C 20 -alkynyl, preferably C 2 -C 10 -alkynyl, such as C 2 -C 4 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-prupinyl, or C 5 -C 7 -alkynyl, such as 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1 Dimethyl-2-propyn
• C3-C15-cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as.
• Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
• Heterocycles five- to twelve-membered, preferably five- to nine-membered, particularly preferably five- to six-membered, oxygen, nitrogen and / or sulfur atoms, ring rings optionally containing several rings such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, Dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
• five- or six-membered saturated nitrogen-containing ring systems which are attached via a ring nitrogen atom and which may contain one or two further nitrogen atoms or another oxygen or sulfur atom.
• C 1 -C 20 -alkoxy denotes a straight-chain or branched alkyl group having 1 to 20
• Carbon atoms (as mentioned above), which are bonded via an oxygen atom (-O-), for example Ci-Cio-alkoxy or Cn-C2o-alkoxy, preferably C1-C10-alkoxy, particularly preferably Ci-C3-alkoxy, such as Methoxy, ethoxy, propoxy.
• oxygen atom for example Ci-Cio-alkoxy or Cn-C2o-alkoxy, preferably C1-C10-alkoxy, particularly preferably Ci-C3-alkoxy, such as Methoxy, ethoxy, propoxy.
• Aryloxy is a mono- to trinuclear aromatic ring system (as mentioned above) which is attached via an oxygen atom (-O-), preferably a mono- to binuclear, particularly preferably a mononuclear aromatic ring system.
• Arylalkyl is a mono- to trinuclear aromatic ring system (as mentioned above) which is attached via a C 1 -C 20 -alkylene group, preferably a mononuclear or dinuclear, more preferably a mononuclear aromatic ring system.
• C 1 -C 20 -alkylene straight-chain or branched hydrocarbon radicals having 1 to 20 carbon atoms, for example C 1 -C 10 -alkylene or C 2 -C 10 -alkylene, preferably C 2 -C 10 -alkylene, in particular methylene, dimethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene ,
• Heteroatoms are preferably oxygen, nitrogen, or sulfur.
• C 1 -C 4 -dialkylamino is a substituted by two, identical or different, straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as mentioned above), for example C 1 -C 4 -dialkylamino or C 3 -C 4 -dialkylamino, preferably C 1 -C 4 -dialkylamino.
• C2-dialkylamino attached via the nitrogen.
• C 3 -C 6 -cycloalkylamine means an amino group substituted with a C 5 -C 6 -cycloalkyl group having 3 to 6 carbon atoms (as mentioned above), for example C 3 -C 4 -cycloalkylamine or C 5 -C 6 -cycloalkylamine, preferably C 5 -C 6 -cycloalkylamine, which is over the nitrogen is attached.
• C 1 -C 4 -dialkylsulfamoyl is an amino group of a sulfonamide which is substituted by two identical or different straight-chain or branched alkyl groups having from 1 to 4 carbon atoms.
• C 1 -C 4 -trialkylammonium denotes an ammonium group which is substituted by three identical or different, straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as mentioned above), for example C 1 -C -trialkylammonium or C 3 -C 4 -trialkylammonium, preferably C 1 -C 2 -Trialkylammonium, which is attached via the nitrogen.
• HO compounds M 3 R 4 R 5 R 6 together are referred to below as "HO compounds.”
• the Cl compounds are preferably used in the process according to the invention
• the Cl compounds and HO compounds are generally known and widely available commercially, or can be the method well known to those skilled in the art.
• the molar ratio is preferably of Cl compounds or HO compounds to compounds of general formula (II) at 10: 1. Particularly preferred at 3: 1 and for example also at 2: 1.
• the compounds of the general formulas (I) and (II) include, of course, in addition to the so-called 2,3-compounds, for example the 2,3-naphthalocyanines or 2,3-anthracyanines, and the so-called isomeric 1, 2 compounds.
• the compounds of the general formulas (I) and (II) can be present in the process according to the invention as acid addition salts of the particular compound or can be prepared.
• mixtures of compounds of the general formula (I) can be obtained by reacting mixtures of compounds of the general formula (II) in the presence of the Cl compounds or HO compounds with the aid of the process according to the invention.
• the proportions of the various compounds of the mixtures which can be used in the process according to the invention are generally arbitrary.
• the molar ratio Vi: V 2 is preferably from 10: 1 to 1:10, more preferably the ratio is from 3: 1 to 1: 3 and in particular 1: 1.
• compounds of the general formula (I) are prepared by the process according to the invention, in which the indices n, m, p and q are all equal to 0 or all equal to 1. Most preferably, the indices n, m, p and q all assume the value O. In in another preferred embodiment, the indices n, m, p and q all assume the value 1.
• the process according to the invention also produces compounds of the general formula (I) in which the symbols R 1 to R 6 are C 1 -C 20 -alkyl, aryl or arylalkyl.
• the symbols R 1 to R 6 are very particularly preferably C 1 -C 20 -alkyl, in particular C 1 -C 10 -alkyl and especially C 4 -C 6 -alkyl.
• compounds of general formula (I) are prepared by the process according to the invention, in which as far as possible all symbols and indices have the preferred or very preferred meanings.
• the compounds of general formula (I) are prepared in the presence of a solvent.
• a solvent In principle, all solvents which are liquid at the temperatures of the process according to the invention are suitable as solvents, in which the substances involved in the reaction in the context of the process according to the invention are at least partially soluble. For example, these solvents have Siedetem- temperatures of about 100 0 C at normal pressure (101, 325 kPa).
• the solutions of the compounds of the general formula (I) in the presence of a solvent used in the process according to the invention may also have the properties of suspensions or dispersions.
• Suitable solvents are, for example, aromatic compounds or dipolar aprotic solvents. Aromatic compounds are preferably used as solvent.
• solvents are toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, quinoline, pyridine or sulfolane. Very particular preference is given to chlorobenzene or pyridine. It is of course also possible to use mixtures of solvents.
• the amount of solvent which can be used in the context of the process according to the invention depends on the solubility of the dissolved compounds and can therefore vary within a wide range.
• the solvent is added in excess (weight ratio).
• the weight ratio of the compounds of general formula (II): solvent is from 1: 2 to 1:20.
• the temperatures which are set for the preparation of the general compounds of the formula (I) by the process according to the invention can in principle vary within a wide range.
• the choice of the temperature range for example, as described above, depends on the solubility of the compounds of the general formulas (I) and (II) and can be determined by the skilled person by simple preliminary experiments. With a higher solubility, for example, lower temperatures for the reaction can be selected in the context of the method according to the invention.
• the temperatures in the process according to the invention are generally selected from the range from 0 ° C. to 200 ° C.
• the temperatures ranging from 20 0 C to 150 0 C. are temperatures in the range of 70 ° C to 140 ° C are very preferably selected.
• the pressure range in which the process according to the invention for the preparation of compounds of the general formula (I) is carried out is variable.
• the inventive method can be carried out at atmospheric pressure, slight negative pressure or overpressure.
• the pressure is selected in the range of 90 kPa to 1000 kPa. Preference is given to a pressure in the range from 100 kPa to 500 kPa.
• the reaction according to the invention of the compounds of general formula (II) is preferably carried out in the presence of the chlorine compounds CI-M 2 R 1 R 2 R 3 and CI-M 3 R 4 R 5 R 6 or hydroxy compounds HO-M 2 R 1 R 2 R 3 and HO-M 3 R 4 R 5 R 6 to compounds of general formula (I) additionally in the presence of a base or a base / water mixture.
• Phase transfer catalysts and their preparation are generally known to the person skilled in the art (R ⁇ MPP Online, "Phase Transfer Catalysis", Georg Thieme Verlag, Document ID RD-16-01507, MJ Dagani, et al., “Bromine Compounds", Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, 2002).
• Many PTK can be purchased.
• tetraalkylammonium salts, phosphonium salts, onium compounds, crown ethers or polyethylene glycols can be used as PTK.
• Preferred PTK are hexaethylguanidinium salts, in particular hexaethylguanidinium chloride, 4-dimethylamino-N- (2-ethylhexyl) pyridinium salts, in particular 4-dimethylamino-N- (2-ethylhexyl) -pyridinium chloride, tetraalkylphosphonium salts, tetraarylphosphonium salts, tris [2- (2-methoxy) ethoxy) ethyl] amine or tetraalkylammonium salts. Furthermore, it is possible to use Aliquat®HTA-1 from Cognis as the PTK.
• Aliquat®HTA-1 is a water-soluble quaternary ammonium salt and is used, for example, in an aqueous solution containing: from 30 to 36% by weight Aliquat®HTA-1, from 50 to 62% by weight water and from 10 to 15 wt .-% NaCl, used.
• hexaethylguanidinium chloride 4-dimethylamino-N- (2-ethylhexyl) - pyridinium chloride, tetraalkylphosphonium salts, tetraarylphosphonium salts, tris [2- (2-methoxy-ethoxy) ethyl] amine used.
• Very preferred is hexaethylguanidinium chloride.
• the amount of PTK used in the process according to the invention can vary within a wide range. Preference is given to using from 0.01 to 10 mol% PTK, based on compounds of the general formula (II).
• the preparation of compounds of the general formula (I) comprises the following steps:
• the partial steps La. until 1.d. The process of the invention can be carried out in any order.
• the addition of the compounds of the general formula (1.a.) before the other steps (1.b. to 1.d., In any order of success) take place.
• the chlorine compounds CI-M 2 R 1 R 2 R 3 and CI-M 3 R 4 R 5 R 6 or hydroxy compounds HO-M 2 R 1 R 2 R 3 and HO- Submit M 3 R 4 R 5 R 6 (1.b.) in a solvent and then follow steps 1.a., 1. ⁇ , and 1.d. in any order.
• the time duration of all time steps 1 to 6 overall, as well as the individual sub-steps is generally of secondary importance.
• the time duration of all time steps together can vary in a wide range from a few minutes up to 24 hours. A longer period of time would be conceivable, but less interesting because of the disadvantageous space-time yield.
• the process may be carried out in any appropriate apparatus well known to those skilled in the art.
• the separation and work-up of the compounds of the general formula (I) it is possible to use any desired methods with which the expert is familiar.
• the separation is carried out by filtration or phase separation.
• the work-up may comprise a purification step, for example washing the compounds of general formula (I) with a liquid, for example methanol, and / or a drying step.
• the compounds of the general formula (II) are prepared by reacting compounds of the general formula (IIIa) to (IIId) comprising the following steps (a) - (d):
• step (a) and (b) of the process according to the invention for the preparation of the compounds of general formula (II) all at the temperatures of this process according to the invention in step (a) and (b) liquid substances are suitable, in which substances involved in the reaction are at least partially soluble.
• the solutions used in the process according to the invention may also have the properties of suspensions or dispersions. It is of course also possible to use mixtures of solvents.
• alcohols in steps (a) and (b) are suitable.
• Preferred solvents are methanol, ethanol, n-propanol, i-propanol, n-butanol, or i-butanol. Most preferably, methanol is used.
• any strong bases or mixtures thereof can be used in step (b).
• preferred strong bases have a pKa of 9 or greater.
• Particularly preferred strong bases are alcoholates, or amines, most preferably sodium methoxide.
• step (c) of the process according to the invention for the preparation of the general compounds of the formula (II) is generally effected as a function of the solubility of the compounds of the general formula (II) and that required for the reaction in step (d) temperatures.
• the other solvent has a higher boiling point than the solvent from step (a), preferably, the other solvent is a high-boiling solvent (boiling point> 100 0 C).
• preference is given to using solvents having a boiling point greater than the temperatures required for the reaction in step (d). It is of course also possible to use mixtures of solvents or mixtures of high-boiling solvents with a base.
• quinoline or a mixture of tetralin and tributylamine can be used as high-boiling solvents (the amount of tributylamine depends on the amount of HCl liberated in step (d)).
• Preference is given to using quinoline.
• the replacement of the solvent from (a) by another solvent, while avoiding separation and / or work-up steps of the compounds formed in step (b), in step (c) of the process described above enables a high yield in the overall process.
• the replacement of the solvent can be carried out in any desired manner, for example continuously or discontinuously.
• the exchange may comprise two steps, namely first removal of the solvent from (a) and secondly addition of the other solvent from (c).
• the removal of the solvent from (a) may be carried out before or after the addition of the other solvent from (c).
• the removal of the solvent from (a) may also be carried out simultaneously with the addition of the other solvent from (c).
• the removal of the solvent from (a) preferably takes place by distillation and the addition of the other solvent from (c) by metering into the reaction vessel.
• the temperatures which are set for the preparation of the general compounds of the formula (II) by the process according to the invention, in particular in step (b) and step (d), can in principle vary within a wide range.
• the choice of the temperature range in step (b) and step (d), for example as mentioned above, will depend on the solubility of the compounds of general formulas (Illa-Illd) and (II).
• the temperature in step (b) generally also depends from the reactivity of the reactants.
• the required temperatures can NEN be determined by the expert by simple preliminary tests. With a higher solubility, for example, lower temperatures for the reaction in step (b) and (d) of the method according to the invention can be selected.
• the temperatures in the process according to the invention are generally selected from the range of 20 ° C. to 250 ° C.
• the temperatures in step (b) in the range from 20 ° C to 150 0 C.
• the temperatures in step (d) in the range of 100 ° C to 250 0 C.
• Very preferred for step (d) from the temperatures range from 120 ° C to 230 ° C INS, particularly from 140 0 C to 220 ° C selected.
• the pressure range in which the process according to the invention for the preparation of compounds of the general formula (II) is carried out is variable.
• the process of the invention can be carried out at atmospheric pressure, slight underpressure, or even overpressure.
• the pressure is selected in the range of 90 kPa to 1000 kPa. Preference is given to a pressure in the range from 100 kPa to 500 kPa.
• step (d) of the process described above is preferably carried out while slowly reaching the reaction temperature and / or under excess pressure.
• time duration of all time steps (a) to (d) as a whole, as well as of the individual substeps, is generally of lesser importance and depends on the temperature.
• the time duration of all time steps together can be in a wide range of a few milli may vary up to 48 hours. A longer period of time would be conceivable, but less interesting because of the disadvantageous space-time yield.
• compounds of the general formula (II) are prepared by the process according to the invention, in which the indices n, m, p and q are all 0 or all equal to 1. Most preferably, the indices n, m, p and q all assume the value 0.
• compounds of general formula (II) are prepared by the process according to the invention, in which the symbols A, A ', A “, D, D', D", E, E ', E “and G, G', G “all the same are CH.
• the present invention also relates to the use of compounds according to the general formula (I) as markers for liquids (use according to the invention), the symbols and indices having the meaning given in the introduction for the formula (I),
• M 1 is Si, not all substituents R 1 to R 3 are simultaneously, and not all substituents R 4 to R 6 are simultaneously, C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, or aryloxy;
• R 1 to R 6 are independently, same or different, C 2 -C 2 o-alkynyl, Cs-ds-cycloalkyl, aryl, aryloxy, trialkylsiloxy, or Ci-C4-trialkylammonium substituted Ci-C2o-alkyl radicals.
• Ci-C2o-alkyl, Ci-C2o-alkoxy, aryloxy, Cs-C ⁇ -cycloalkylamino, five- or six-membered saturated nitrogen-containing ring systems which are attached via a ring nitrogen atom and which contain one or two further nitrogen atoms or another oxygen or sulfur atom R 1 to R 6 may be the same or different,
• R 1 to R 6 independently of one another, identical or different, are C 1 -C 20 -alkyl, aryl, C 1 -C 20 -alkoxy, aryloxy,
• R 1 to R 6 independently of one another, the same or different
• the invention therefore also relates to compounds of the general formula (I) in which the symbols and indices have the following meanings:
• Suitable liquids which can be labeled by means of the compounds of the general formula (I) according to the process according to the invention are in particular water or organic liquids, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, Isopentanol, neopentanol or hexanol, glycols, such as 1, 2-ethylene glycol, 1, 2 or 1, 3 Propylene glycol, 1,2,3,3 or 1,4-butylene glycol, di- or triethylene glycol or di- or tripropylene glycol, ethers, such as methyl tert-butyl ether, 1,2-ethylene glycol mono- or dimethyl ether, 1, 2-ethylene glycol mono- or diethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran or dioxane, ketones, such as
• the compounds of the general formula (I) are used particularly advantageously in accordance with the novel process for the marking of oils, in particular mineral oils, preferably of additive concentrates.
• the invention furthermore relates to liquids, preferably oils, in particular mineral oils, which contain at least one compound of the general formula (I) as a marker.
• the compounds of the general formula (I) to be used as markers are added to the liquids in amounts such that reliable detection is ensured.
• the (weight related) total content is at markers in the labeled liquid about 0.1 to 5000 ppb, preferably 1 to 2000 ppb and more preferably 1 to 1000 ppb.
• the compounds are generally added in the form of solutions (stock solutions).
• suitable solvents for preparing these stock solutions are preferably aromatic hydrocarbons, such as toluene, xylene or higher-boiling aromatic mixtures.
• a total concentration of the marking substances of from 0.5 to 50% by weight, based on the total weight of these stock solutions, is generally selected.
• the compounds of the general formula (I) can also be used in combination with other marking substances / dyes.
• the total amount of the marking substances in the liquids is then usually in the range described above.
• the invention also provides a process for the labeling of liquids, preferably oils, in particular mineral oils, preferably of additive concentrates, wherein the liquid is a compound of general formula (I) is added.
• the invention also provides a method for the detection of markers in liquids containing at least one compound of general formula (I).
• the detection of the compounds of the general formula (I) in the liquids is carried out by customary methods. Since these compounds usually have high absorbency and / or fluorescence, in the given case, e.g. a spectroscopic detection.
• the compounds of the general formula (I) generally have their absorption maximum in the range from 600 to 1000 nm and / or fluoresce in the range from 600 to 1200 nm and can thus easily be detected with suitable instruments.
• the detection can be carried out in a manner known per se, for example by measuring the absorption spectrum of the liquids to be examined.
• ⁇ ma ⁇ means the wavelength of the longest wavelength absorption maximum of the marker.
• the wavelength of the maximum emission is usually in the range of 620 to 900 nm.
• the fluorescent light thus generated is advantageously detected with a semiconductor detector, in particular with a silicon photodiode or a germanium photodiode.
• Detection succeeds particularly advantageously if an interference filter and / or an edge filter (with a short-wave transmission edge in the range from ⁇ ma ⁇ to ⁇ ma ⁇ +80 nm) and / or a polarizer are also located in front of the detector.
• a preferred method for detecting labels in liquids containing at least one compound of general formula (I) in an amount sufficient to induce detectable fluorescence upon irradiation with radiation of a suitable wavelength is carried out by: a) subjecting the liquid to Electromagnetic radiation of a wavelength of 600 to 1000 nm is irradiated and b) the excited fluorescence radiation is detected with a device for detecting radiation in the range of 600 to 1200 nm.
• Another preferred method for the detection of markers in liquids which contain at least one compound of general formula (I) in an amount sufficient to show detectable absorption upon irradiation with radiation of a suitable wavelength is carried out by: a) the liquid with electromagnetic radiation of a wavelength of
• the invention also provides a process for the identification of liquids, preferably oils, in particular mineral oils, preferably of additive concentrates, which contain a compound of general formula (I) in an amount which is detectable upon irradiation with a suitable wavelength Fluorescence, wherein a) the liquid with electromagnetic radiation of a wavelength of
• the absorption of the electromagnetic radiation a) is detected with a device for the detection of radiation and c) the excited fluorescence radiation is detected with a device for the detection of radiation in the range from 600 to 1200 nm and d) the liquid is identified by means of the absorption b) and / or fluorescence c) and e) the concentration of the compound of the general formula (I) in the liquid is determined with the aid of the fluorescence radiation c).
• the measurement data from steps b) and e) of the method are linked in order to carry out the identification.
• the identification may contain as a further step the comparison with known spectroscopic data.
• the known spectroscopic data are electronically stored spectra which can be stored, for example, in data beacons.
• the compounds of the general formula (I) can also be used as a component in additive concentrates (hereinafter also referred to as "packagings"), which in addition to a carrier oil and a mixture of different fuel additives generally also include dyes and, for the invisible fiscal or manufacturer-specific marking, additionally contain markers.
• packages enable various mineral oil distribution companies to supply themselves from a “pool” of unadditized mineral oil and only with the aid of their individual packages to supply the mineral oil, e.g. during filling into appropriate transport containers, which give company-specific additives, colouration and marking.
• Packages according to the invention then contain as components in particular: a) at least one compound of the general formula (I), b) at least one carrier oil, c) at least one additive selected from the group consisting of i. Detergents, ii. Dispersants and iii. Valve seat wear-inhibiting additives, d) and optionally further additives and auxiliaries.
• the concentration of component a), i. the at least one compound of the general formula (I) in the packages according to the invention is usually selected at a level such that after addition of the package to the mineral oil the desired concentration of marking substance (s) is contained therein.
• Typical concentrations of the marking substances in the mineral oil are approximately in the range of 0.01 to a few 10 ppm by weight.
• Component b), ie the at least one carrier oil, is usually in the packages in a concentration of 1 to 50, in particular 5 to 30 wt .-%, and component c), ie the at least one detergent and / or the at least one dispersant, usually in a concentration of 25 to 90% by weight, in particular 30 to 80% by weight, in each case based on the total amount of components a) to c) and optionally d), wherein the sum of the individual concentrations of the components a) to c) and optionally d) to 100 wt .-% complements.
• corrosion inhibitors, antioxidants or stabilizers, demulsifiers, antistatic agents, metallocenes, lubricity improvers and amines for lowering the pH of the fuel are contained in the packages, their total concentration usually amounts to not more than 10% by weight. %, based on the total amount of the package (ie the total amount of components a) to c) and d)), wherein the concentration of the corrosion inhibitors and demulsifiers usually in the range of about 0.01 to 0.5 wt. % of the total amount of the package.
• organic solvents are contained in the packages, their concentration in the sum usually amounts to not more than 20 wt .-%, based on the total amount of the package.
• solvents are usually derived from solutions of the markers and / or dyes which are added to the packages in the interests of more accurate metering, in place of the pure tags and / or dye.
• component d If, as component d), other markers other than the compounds of the general formula (I) are contained in the packages, their concentration is again measured at the content which they should have after addition of the packages in the mineral oil. The same applies to component a). If dyes are present in the packages according to the invention as component d), their concentration is usually about between 0.1 to 5 wt .-%, based on the total amount of the package.
• the present invention provides efficient labeling methods of preparation. Furthermore, markers were found which are characterized by good long-term stability in the liquids to be marked, in particular oils, mineral oils or additive concentrates.
• nm nanometers
• UVA / is (toluene): UVA / is spectrum in the wavelength range from 300 nm to
• ⁇ max wavelength longest wavelength absorption maximum in nm.
• the reaction mixture was refluxed for a total of six hours (132 ° C.), after which, after one and two hours, 1.21 g (5.0 mmol) of 97% by weight of tri-n-butylchlorosilane were added. After cooling the solution to room temperature, the solution was filtered. The filtrate was concentrated to dryness. The residue was stirred with 10 ml of methanol, filtered off with suction, washed with methanol and water and dried at 50 ° C. under reduced pressure. There were obtained 3.78 g of blue powder, which contained 95 mol% of valuable material compared to a pure substance after UVA / is. The recycling yield was 79% d. Th ..
• Example 5 Preparation of a mixture of silicon phthalocyanine bis (tri-n-hexylsilyloxide), tri-n-butylsilyloxide-tri-n-hexylsilyloxide and bis (tri-n-butylsilyloxide)
• Example 8 Preparation of a mixture of silicon phthalocyanine bis (tri-n-hexylsilyloxide), tri-n-hexylsilyloxide-tri-n-phenylsilyloxide and bis (triphenylsilyloxide)
• Example 1 Preparation of silicon phthalocyanine bis (diisobutyl octadecylsilyloxide)
• Example 16 Silicon naphthalocyanine bis (trihexylsilyloxide)
• Comparative Example 17 1 (4), 8 (11), 15 (18), 22 (25) -tetra (3-methylpiperidino) phthalocyanine
• Example 19 Preparation of a mixture of silicon naphthalocyanine bis (tri-n-hexylsilyloxide), tri-n-butylsilyloxide-tri-n-hexylsilyloxide and bis (tri-n-butylsilyloxide)

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