MXPA99010161A - Phthalocyanine and use of phthalocyanine as a marking agent - Google Patents

Abstract

The invention relates to phthalocyanine of formula (I), wherein Me means twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AlCl, AlOH, AlOCOCH3, AlOCOCF3, SiCl2 or Si(OH)2, at least four of the radicals R1 to R16 independently mean a five or six-membered saturated nitrogenous heterocyclic radical which is bonded to the phthalocyanine sceleton by a cyclic nitrogen atom and may contain other heteroatoms, and optionally, the remaining radicals R1 to R16 mean hydrogen, halogen, hydroxy sulfonyl or C1-C4 dialkyl sulfamoyl, with the exception of tetrakispiperidinyl phthalocyanine. The invention also relates to the use of phthalocyanines substituted by heterocyclic radicals for marking liquids such as mineral oils which contain phthalocyanines of this type.

Description

FTALOCIANINS AND USE THEREOF AS MARKERS The present invention relates to novel phthalocyanines of the formula I where Me is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, UNC1, A1C1, AlOH, A10C0CH3 / A10C0CF3, SiCl2 or Si (OH) 2, at least four of the radicals R1 to R16 are each, independently of the others, a heterocyclic radical containing five or six membered saturated nitrogen attached to the phthalocyanine structure through a ring nitrogen atom and which may also contain one or two additional nitrogen atoms or an additional oxygen or sulfur atom, the remaining radicals R 1 to Rld are each hydrogen, halogen, hydroxysulfonyl or C 1 -C 4 -sulfamoyl dialkyl, provided that tetrakispiperidinylphthalocyanine is excluded. to the use of heterocyclyl substituted phthalocyanines to mark liquids, and to mineral oils containing such phthalocyanines. J. Gen. Chem. USSR, 51 (1981), 1405-1411, teaches the preparation of tetrakispiperidinylphthalocyanine. WO-A-94/02570 and WO-A-96/10620 describe phthalocyanines as markers for liquids, especially mineral oils. However, it has been found that the markers described there still have defects in terms of their application properties, especially insufficient solubility and insufficient chemical stability in solution. It is an object of the present invention to provide suitable phthalocyanines that have an improved property profile. We have found that this object is achieved through the phthalocyanines of formula I more particularly defined at the beginning. Any alkyl that appears in the formulas mentioned herein may be straight or branched chain. Halogen is, for example, fluorine, chlorine, bromine or iodine.

A C? -C-sulfamoyl dialkyl is, for example, dimethylsulphamoyl, diethylsulphamoyl, dipropylsulfane, diisopropylsulphamoyl, dibutylsulphamoyl or N-methyl-N-ethylsulphamoyl. Heterocyclic radicals containing saturated nitrogen of five or six suitable members which are fixed on the structure of the phthalocyanines via a ring nitrogen atom and may also contain one or two additional nitrogen atoms or an oxygen or sulfur atom Additional in the ring are derivatives, for example, of pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isoxazolidine, piperidine, piperazine, morpholine or thiomoforline as the basic structure. The heterocyclic radicals can be monosubstituted or polysubstituted, preferably monosubstituted, disubstituted or trisubstituted, especially monosubstituted. Preferred substituents are Ci-C4 alkyl, benzyl, phenylethyl or phenyl. Suitable heterocyclic radicals are, for example, pyrrolidin-1-yl, 2- or 3-? T? Ethylpyrrolidin-1-yl, 2,4-dimethyl-3-ethylpyrrolidinyl, pyrazolidin-1-yl, 2-, 3- 4- or 5-methylpyrazolidin-1-yl, imidazolidin-1-yl, 2-, 3-, 4- or 5-methylimidazolidin-1-yl, oxazolidin-3-yl, 2-, 4- or 5-methyloxazolidin-3-yl, isoxazolidin-2-yl, 3-, 4- or 5-methylisoxazolidin-2-yl, piperidin-1-yl, 2-, 3-, 4-methyl-, -ethyl- or either -benzyl-piperidin-1-yl, 2,6-dimethylpiperidin-1-yl, piperazin-1-yl, 4- (Ci-C4 alkyl) piperazin-1-yl, such as 4-methyl- or 4- ethylpiperazin-1-yl, morpholin-4-yl, thiomorpholin-4-yl or S, S-thiomorpholin-4-yl dioxide. Preferred heterocyclic radicals are derived from pyrrolidine, piperidine, piperazine or morpholine as the basic structure. The phthalocyanines of the formula I are preferred where four of the radicals R1 to R16 are each heterocyclic radical.

Further preferred are phthalocyanines of the formula I wherein four of the radicals R1 to R16 are each a heterocyclic radical and the remaining radicals R1 to R16 are each hydrogen. Preferred are phthalocyanines of the formula I having monosubstituted or polysubstituted heterocyclic radicals, preferably monosubstituted, disubstituted or trisubstituted, especially monosubstituted, by C 1 -C 4 alkyl, benzyl, phenylethyl or phenyl. Phthalocyanines corresponding to the formula are preferred where the radicals R4, R8, R12 and R16 and also R2,. R6, R10 and R14 are each a heterocyclic radical and Me is, in each case, in accordance with that defined above, and also their positional isomers in relation to the radicals R4, R8, R12 and R16 and also R2, Rd, R10 and R14. Of particular interest are phthalocyanines of the formula Ia or Ib, where R4, R8, R12 and R16 and also R2, R6, R10 and R14 are each pyrrolidin-1-yl, piperidin-1-yl, piperazin-1-yl or morpholin-4-yl, said radicals may be monosubstituted, disubstituted or trisubstituted, preferably monosubstituted, by C 1 -C 4 alkyl, benzyl, phenylethyl or phenyl. Also preferred are phthalocyanines of the formula I in which the substituents are selected from a combination of the aforementioned preferred substituents. The novel phthalocyanines of the formula I can be obtained in conventional manner, for example, in accordance with that described in J. Gen. Chem. USSR 51 (1981) '1405-1411, FH Moser, AL Thomas, The Phthalocyanines, CRC Press, Boca Rota, Florida, 1983, or J. Am. Chem. Soc. 106 (1984) 7404-7410, for example, phthalonitriles which, in accordance with formula I, carry suitable substituents can react in an inert diluent in presence of a base, optionally in the presence of a metallizing reagent.

The present invention also offers the use of phthalocyanines of the formula where Me is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel VO, uncle, A1C1, AlOH, A10COCH3, AIOCOCF3, SiCl2 or Si (OH) 2, at least four of the radicals R1 to Rld are, each, independent of the others, a heterocyclic radical containing five or six membered saturated nitrogen, which is attached on the phthalocyanine structure through a ring nitrogen atom and which may also contain one or two additional nitrogen atoms or an additional oxygen or sulfur atom, and the remaining radicals R1 to Rld are each hydrogen, halogen, hydroxylsulfonyl or dialkyl C? -C4-sulfosyl, as markers for liquids. The use of phthalocyanines of the formula I is preferred where four of the radicals R1 to R16 are each a heterocyclic radical. It is further preferred to use phthalocyanines of the formula I where four of the radicals R1 to R16 are each a heterocyclic radical and the remaining radicals R1 to Rld are each hydrogen. Further preferred is the use of phthalocyanines of the formula I which have mono- or polysubstituted heterocyclic radicals, preferably -monosubstituted, disubstituted or trisubstituted, -especially monosubstituted, by C 1 -C 4 alkyl / benzyl, phenylethyl or phenyl. It is especially preferred to use phthalocyanines corresponding to the formula Ib or (la) (Ib) where the radicals R4, R8, R12 and Rld and also R2, Rd, R10 and R14. Each is a heterocyclic radical, and Me is, in each case, in accordance with what is defined above, and also its positional isomers in relation to the radicals R, R, R and R and also R2, R6, R10 and R14. Especially interesting is the use of phthalocyanines of the formula Ia or Ib, where R4, R8, R12 and R15 and also R2, Rd, R10 and R14 are each pyrrolidin-1-yl, piperidin-1-yl, piperazin-1 -yl or morpholin-4-yl, said radicals may be monosubstituted, disubstituted or trisubstituted, preferably monosubstituted, by C 1 -C 4 alkoyl, benzyl, phenylethyl or phenyl. It is often necessary to mark liquids with the object that the liquids marked in this way can be detected after, for example, in use, through appropriate methods. In this way, it is possible, for example, to distinguish fuel and diesel. Suitable solvents for marking in accordance with the present invention through the more particularly defined compounds above are especially 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-, 2,3- or 1 , -butylene glycol, di- or triethylene glycol or di- or tripropylene glycol, ethers such as methyl tert-butyl ether, monomethyl or dimethyl ether of 1,2-ethylene glycol, monoethyl or diethyl ether of 1,2-ethylene glycol, -methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran or dioxane, ketones, such as ketones, methyl ethyl ketone or diacetone alcohol, esters, such as methyl acetate, ethyl acetate, propyl acetate, or butyl acetate, aliphatic hydrocarbons or aromatics such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, mineral spirits, mineral oils, such as gasoline, kerosene, diesel oil or fuel oil, natural oils , such as olive oil, soybean oil or sunflower oil, or natural or synthetic oils for engines, hydraulics or gears, for example motor vehicle oil or sewing machine oil, or brake fluids. The aforementioned compounds are especially useful for marking mineral oils where some form of identification is required, for example, for tax reasons. To keep the costs of this marking at a minimum level, it is usually desirable to employ very high performance dyes for coloring. However, even these dyes known as strong dyes can no longer be detected purely visually in high dilution in mineral oils.Based on the weight of the liquid to be labeled, 1 to 1000 ppb, preferably 1 to 500 ppb, especially 100 ppb to 500 ppb, of phthalocyanine II are used. In order to mark liquids, especially mineral oils, the phthalocyanines of formula II are generally used in the form of solutions. Suitable solvents are preferably aromatic hydrocarbons such as aromatic hydrocarbons substituted by C.sub.1 -C.sub.20 alkyl such as toluene, xylene or Shellsol.RTM. (From Shell). To prevent the resulting solutions from having too high a viscosity, the concentration of phthalocyanine II is generally chosen within the range of 0.5 to 60% by weight, based on the solution. The present invention also offers mineral oils comprising one or more phthalocyanines of the formula II. - Phthalocyanines II generally have their maximum absorption within the range of 600 to 1200 nm and / or fluoresce that within the range of 620 to 1200 nm and are therefore easy to detect by the use of suitable instruments. The detection of phthalocyanines II can be achieved in conventional manner, for example, by measuring the IR absorption spectrum of the liquids to be examined. However, it is also possible to excite the fluorescence of the phthalocyanines II present in the liguids, advantageously by using a semiconductor laser or a semiconductor diode. It is especially advantageous to employ a semiconductor laser or semiconductor diode having a maximum emission wavelength within the region, spectral lambdamax-100 nm at lambdamax + 20 nm. Here, lambdamax is the wavelength of the absorption maximum of the marker. The maximum editing wavelength is found, '/ within the range of 620 to 1200 nm. The fluorescent light generated in this way is advantageously detected by the use of a semiconductor detector, especially with a silicon photodiode or a germanium photodiode. The detection is achieved in a particularly advantageous manner when the detector is placed behind an interference filter and / or a cut filter (which has a short wave transmission cut within the range of lambdamax to lambdamax + 80 nm) and / or a polarizer. Through the aforementioned compounds, it is very easy to detect the labeled liquids, even if the phthalocyanines II are present only in a concentration of approximately 1 ppm (detection by absorption) or approximately 5 ppb (detection by fluorescence). The phthalocyanines of the formula II are highly soluble in the liquids to be labeled. They also have a high chemical stability in solution. - The following examples illustrate the invention. A) Preparation Example 1 56.3 g (0.325 mol) of a solution of 30% by weight methanolic sodium methoxide in 1 1 of n-butanol was dissolved and the excess methanol was removed by distillation until obtaining a boiling point constant of 117 ° C. 112.5 g of 3- (3'-methylpiperidin-1-yl) phthalonitrile were then added and the mixture was stirred under reflux for 6 hours. It was then added to 1.5 l of methanol, and the mixture was subsequently stirred for 1 hour and filtered with suction. The residue was washed in succession with methanol, water and acetone and then air dried. 101.4 g of phthalocyanine of the formula were obtained where PcH2 is the quadrivalent radical of phthalocyanine whose central unit is twice hydrogen. The same method provides the phthalocyanines mentioned below in Table 1. Table 1"PcMe (R) 4 11 lication I. Detection by absorption in the IR region Sufficient dye of the formula was dissolved in one of the liquids mentioned in Table 2 to obtain a solution having a dye content of 10 ppm. The absorption of these solutions in the IR region was measured in each case by means of a commercially available spectrometer (1 cm cell). Table 2 Dye content maximum absorption absorption (ppm) (nm) fuel for diesel engine 1.10 762 unleaded gasoline 1.10 760 ethanol 1.05 771 toluene 1.15 770 To measure the stability of the colorant in storage, the samples were stored for several weeks at room temperature (RT) and at 50 ° C, and the absorption was measured using a commercially available spectrometer. Specifically, the results obtained were the following: Table 3 Duration of Ethanol toluene fuel for gasoline Test (Temp.) Diesel engine without lead time 0 (RT) 1.0535 1.1486 1.0964 1.0993 1 week (RT) 1.0601 1.152 1.0977 1.0937 2 weeks (RT) 1.0479 1.1484 1.097 1.1014 4 weeks (RT) 1.0467 1.1517 1.097 1.098 8 weeks (RT) 1.0181 1.1443 1.078 1.0869 1 week (50 ° C) 1.0467 1.1421 1.016 1.0926 2 weeks (50 ° C) 1.0521 1.1538 1.0917 1.0989 4 weeks (50 ° C) 1.043 1.1438 1.0937 1.0864 8 weeks (50 ° C) 1.0467 1.1445 1.0455 1.0617 II. Detection by fluorescence in the NIR region The fluorescence of the marker is excited using the emission of a commercial semiconductor diode laser. The parallel laser beam is directed in the sample in a 1 cm cell. To double the excitation intensity, the transmitted lux ray is reflected by a mirror and passed through the sample again. The "fluorescent" light is represented in the form of an image by means of optical elements (lens system) in the detector, a silicon photodiode, and the light emitted towards the back is directed in the same way in the silicon photodiode by means of A concave mirror The interfering light (scattered excitation light) is removed from the fluorescent light by the use of cut-off and / or interference filters and / or polarizer (NIR polarization film).

The polarizer is optimized in such a way that the direction of maximum transmission is perpendicular to the plane of polarization of the excitation light. Sufficient coloring of the formula was dissolved in diesel engine fuel to obtain a solution that has a dye content of 250 ppb. This solution was measured by means of the general method II using the following apparatus parameters: excitation: pleasure of semiconductor diode of a laser wavelength of 789 nm; CW 2 W power (modulation: 1.9 kHz). Filter: long-pass interference filter 805 nm. Photodetector: silicon PIN diode of an area of cm2. the photocurrent was detected using a synchronous amplifier. The essential aspect of these measurements was the stability of the colorant in storage at room temperature. The measurements obtained appear in Table 3. Table 3. Absorbance time to fluorescence signal (weeks) lambdamax (nm) (in scale divisions) 0 789 1.96 1 789 1.98 2 789 2.04 3 789 1.90 4 789 1.95 15 20 25

Claims (1)

1. CLAIMS Phthalocyanines of the formula I where Me is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, UNCLE, AlCl, AlOH, A10C0CH3, AIOCOCF3, SiCl2 or Si (OH) 2, at least four of the radicals R1 to Rld are , each, independently of the others, a heterocyclic radical containing nitrogen that is monosubstituted or polysubstituted by C 1 -C 4 alkyl, benzyl, phenylethyl or phenyl and is attached to the phthalocyanine structure through a ring nitrogen atom and is derived from pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isoxazolidine, piperidine, piperazine, morpholine or thiomorpholine, and the remaining radicals R1 to R16 are each hydrogen, halogen, hydroxysulfonyl or dialkyl C? -C4-sulfamoyl. Phthalocyanines according to claim 1, wherein four of the radicals R1 to R16 are each a heterocyclic radical. Phthalocyanines according to claim 1, wherein four of the radicals R 1 to Rld are each a heterocyclic radical and the remaining radicals R 1 a R16 are, each, hydrogen. Phthalocyanines according to claim 1, according to formula I or Ib where the radicals R% RB, R1¿ and R16, and also R% R6, R1U and R14 are each, a heterocyclic radical and Me is, in each case, in accordance with what is defined above, and also their positional isomers in relation to the radicals R4, R8, R12 and Rld, and also R2, R6, R10 and R14. The use of phthalocyanines according to claim 1 as markers for lipids. The use according to claim 1 of phthalocyanines as markers for mineral oils. mineral ceites comprising one or more phthalocyanines according to the provisions of claim 1.