Phthalocyanines

FIELD: organic chemistry, metalloorganic compounds.

SUBSTANCE: invention describes phthalocyanines of the formula (I): wherein me means lithium twice, AlCl, AlOH, AlOCOCF3 or SiCl2; four radicals among from R1 to R16 comprise independently of one another nitrogen atom, heterocyclic radical substituted once or some times with (C1-C)-alkyl, benzyl, phenylethyl or phenyl and bound with skeleton (carcass) of phthalocyanine through a ring nitrogen atom and represents residue of pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isoxazolidine, piperidine, piperazine, morpholine or thiomorpholine, and other radicals from R1 to R16 mean hydrogen atom. Compounds can be used as agents for marking of liquids, in particular, mineral oils.

EFFECT: valuable properties of compounds.

3 cl, 1 tbl, 2 ex

 

The invention relates to new organic compounds that can be used for marking liquids, and more particularly to a phthalocyanines.

From European application EP 0190444 A1 from 13.08.1986, known phthalocyanines of the formula (A)

in which

Me means twice Nickel, VO, or TiO,

at least four of the radicals R1-R16independently of one another are nitrogen-containing heterocyclic radical, associated with phtalocyanines skeleton via a nitrogen atom of the ring, and, if necessary, the remaining radicals R1-R16are hydrogen or an organic residue, which can be used as a light absorbent layer, supported on a carrier of the optical recording medium.

From the publication J.Gen. Chem. USSR, vol. 51, str to 1411, 1981, known getting tetracosapentaenoic.

The closest analogue of this invention is the patent RU 2 076 127 C1 from 27.03.1997, from which known phthalocyanines above formula (A), in which

Me means twice hydrogen, magnesium, zinc, copper,

the radicals R1-R16independently are a hydrogen atom or nitrogen-containing 5 to 7-membered heterocyclic ring which may be substituted by alkyl and through a ring nitrogen atom linked to the phthalocyanine skeleton, which can be used is La labelling of blood.

The disadvantages of these phthalocyanines are that they exhibit low solubility and lack of chemical stability in solution.

The objective of the invention is the provision of new phthalocyanines with improved properties that can be used for marking liquids, in particular mineral oils.

The problem is solved by the phthalocyanines of the formula (I)

in which

Me means twice lithium, AlCl, AlOH, AlOCOCH3, AlOCOCF3, SiCl2or Si(OH)2,

at least four of the radicals R1to R16denote independently from each other nitrogen-containing, heterocyclic radical, which is substituted one or more times With1-C4-alkyl, benzyl, Venetian or phenyl and through a ring nitrogen atom is linked to the skeleton (skeleton) phthalocyanine and removed from pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isoxazolidine, piperidine, piperazine, research or thiomorpholine, and

the other radicals R1to R16does not necessarily signify hydrogen, halogen, oxycarbonyl or1-C4-dialkylamino.

Preferably the phthalocyanine of formula (I) can be used as a means for marking mineral oils.

Suitable heterocyclic radicals are, is, for example, pyrrolidin-1-yl, 2 - or 3-methylpyrrolidine-1-yl, 2,4-dimethyl-3-ethylpyrrolidin, pyrazolidine-1-yl, 2-, 3-, 4 - or 5-methyl-pyrazolidine-1-yl, imidazolidin-1-yl, 2-, 3-, 4 - or 5-methyl-imidazolidin-1-yl, oxazolidin-3-yl, 2-, 4 - or 5-methyloxazolidine-3-yl, isoxazolidine-2-yl, 3-, 4 - or 5-methyl-isoxazolidine-2-yl, piperidine-1-yl, 2-, 3-, 4-methyl-, -ethyl or-benzylpiperidine-1-yl, 2,6-dimethylpiperidin-1-yl, piperazine-1-yl, 4-(C1-C4-alkyl)piperazine-1-yl, such as 4-methyl - or 4-ethylpiperazin-1-yl, morpholine-4-yl, thiomorpholine-4-yl or thiomorpholine-4-yl-S,S-dioxide.

Preferred heterocyclic radicals are remnants of pyrrolidine, piperidine, piperazine or research.

Preference is given also to the phthalocyanines of the formula I, in which four of the radicals R1-R16mean above-mentioned heterocyclic radical.

In addition, the preferred phthalocyanines of the formula I, in which four of the radicals R1-R16mean above-mentioned heterocyclic radical and the remaining radicals R1-R16mean hydrogen.

Further preferred phthalocyanines of the formula I, which have the above-mentioned heterocyclic radicals, substituted one or more times, preferably one to three times, in particular once1-C4-alkyl, benzyl, ventilation or phenyl.

Special article the penalty preferred phthalocyanines, follow the formula Ia or IB

in which the radicals R4, R8, R12or R16and R2, R6, R10and R14means each of the above heterocyclic radical and Me is the above value, as well as their isomers provisions of the radicals R4, R8, R12and R16and R2, R6, R10and R14.

Of particular interest are phthalocyanine formula Ia or IB, in which R4, R8, R12and R16and R2, R6, R10and R14mean every pyrrolidin-1-yl, piperidine-1-yl, piperazine-1-yl or morpholine-4-yl, and these radicals can be from one to three times, preferably once, substituted C1-C4-alkyl, benzyl, ventilation or phenyl.

Along with this preferred phthalocyanines of the formula I in which the substituents are selected from the combination of the above preferred substituents.

New phthalocyanines of the formula (I) can be obtained in a known manner, for example, described in the publications J.Gen.Chem. USSR, vol. 51, str to 1411, F.H.Moser, A.L.Thomas "The Phthalocyanines, CRC Press, Boca Rota, Florida, 1983, or J. Am. Chem. Soc., volume 106, str to 7410, 1984.

Suitable of liquid and, which can be labelled according to the invention using the above compounds are, in particular, organic liquids, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, Isobutanol, sec.-butanol, pentanol, isopentanol, neopentane or hexanol, glycols, such as 1,2-ethylene glycol, 1,2 - or 1,3-propylene glycol, 1,2-, 2,3 - or 1,4-butyleneglycol, di - or triethylene glycol or di - or tripropyleneglycol, ethers, such as methylene-Deut.-butyl ether, 1,2-etilenglikolevye or dimethyl ether, 1,2-etilenglikolevye or diethyl ether, 3-methoxypropanol, 3-isopropoxyphenol, tetrahydrofuran or dioxane, ketones, such as acetone, methyl ethyl ketone or diacetone-alcohol, esters such as methyl ester acetic acid, ethyl ester acetic acid, propyl ester acetic acid or butyl ester of acetic acid, aliphatic or aromatic hydrocarbons, such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, test gasoline, mineral oil, such as gasoline, kerosene, diesel and boiler fuel, natural oils, such as olive oil, soybean oil or sunflower oil, or natural or synthetic engine, hydraulic or gear oils, such as oil is to a car engine or sewing machines or brake fluid.

Especially preferably can be applied to the above compounds for marking mineral oils, which simultaneously requires the identification, for example, for tax reasons. To keep the cost of such identification as low as possible, usually try to apply for colouring efficiently paint. However, even the so-called crosscontinent paint at high dilution in mineral oils are often no longer perceived visually.

In terms of the weight to be marking fluid used from 1 to 1000 ppm billion, preferably from 1 to 500 ppm billion and, in particular, from 100 to 500 ppm billion phthalocyanine of the formula (I).

For marking liquids, in particular mineral oils, phthalocyanines of the formula (I) can be applied in General in the form of solutions. As a suitable solvent, preferably aromatic hydrocarbons, such as toluene, xylene or Shellsol® (shell). To prevent too high viscosity of the obtained solutions are usually selected concentration of phthalocyanine (I) from 0.5 to 60 wt.% in terms of the solution.

The phthalocyanines of the formula (I) are, as a rule, its maximum absorption in the range from 600 to 1200 nm and/or fluoresce in the range from 620 to 1,200 nm and therefore can be easily recognized by appropriate tools.

You can also excite the fluorescence present in the fluids phtalocyanines a semiconductor laser or a semiconductor diode. Of particular advantage is the use of a semiconductor laser or a semiconductor diode with a wavelength of maximum emission in the spectral range from λmax-100 nm to λmax+20 nm. λmaxmeans at the wavelength of maximum absorption of the marking substance. The wavelength of maximum emission is thus 620 to 1200 nm.

Thus obtained fluorescent light is detected by a semiconductor detector, in particular silicon or germanium photodiode.

Particularly well able to carry out the detection, if the detector is interference filter and/or edge filter (wavelength transmission edge in the range from λmaxto λmax+80 nm) and/or a polarizer.

Using the above compounds is possible in a simple way to detect the marked fluid, even if phthalocyanines (I) are only present in a concentration of approximately 1 part./million (detection by absorption) or approximately 5 ppm billion (detectie fluorescence).

The phthalocyanines of the formula (I) are distinguished by good R is stoimosti to be labeled liquids. In addition, they have high chemical stability in solution.

The following examples explain in detail the invention.

A) Obtaining phtalocyanines formula (I).

Phthalodinitrile, bearing in accordance with the formula (I) suitable substituents, is subjected to reaction in an inert diluent in the presence of a base and optionally in the presence of a suitable means of metallization.

The above given are shown in table 1 phthalocyanines.

Table 1
PcMe(R)4
Example No.MeR
1AlCl
2AlCl
3AlCl
4AlCl
5AlCl
6SiCl2
7SiCl2

Table 1 (continued)
8AlOCOCF3
9AlOH
10AlCl
11AlOCOCF3
12SlCl2

Offer phthalocyanines of General formula (I) can be used for marking liquids, in particular mineral oils, and detection is as follows.

I. Detection by absorption in the range of infrared radiation.

In liquids, such as, for example, diesel fuel, free from lead-free gasoline, ethanol and toluene, dissolve as much of the dye of the formula (I)that receive the solution with the content of the dye in 10 frequent./million the absorbance of these solutions in the range of infrared radiation is measured using a commercially available spectrometer (1 cm cuvette). Were obtained distinct absorption maxima.

To measure the stability during storage of the dye samples stored for several weeks (up to 8 weeks) at room temperature and at 50°and measure the absorption of using a conventional, commercially available spectrometrybased results for the liquids used mostly show a constant value acquisitions during this experience.

II. Detection by fluorescence in the range of near infrared radiation.

For fluorescence excitation of the marker using the emission semiconductor laser diode. The parallel laser beam is directed to 1-cm cuvette sample. To double the intensity transmittere beam of light reflektiert mirror and again passed through a sample.

Fluorescent light is depicted using an optical element (lens system) on the detector silicon photodiode. Reflecting on the reverse side of the light is directed hollow mirror also on a silicon photodiode.

To separate the interfering light (scattered excitation light from the fluorescent light used edging and/or interference filter and/or a polarizer (polarization film to work in the range of near infrared radiation).

Optimization of the polarizer is selected when you do this so that the direction of maximum emission perpendicular to the plane of polarization of excitation light.

Diesel fuel is dissolved is the amount of dye of the formula (I)that receive the solution with the content of the dye in 250 ppm billion.

This solution is measured according to the above data when using the following devices.

Excitation: the laser is a semiconductor diode with a wavelength of 789 nm; power is not the reading issue: 2 MLT (modulation: 1,9 kHz).

Filter: long indifferently filter 805 nm.

Detector: Silicon PIN diode with a surface of 1 cm2. The photocurrent detected by the amplifier. An essential aspect of this dimension is the storage stability of the dye at room temperature. Received a distinct dimension values.

Additional example 2.

In nitrogen atmosphere to 200 ml of 1-pentanol add 0.9 g (0.13 mol) of lithium and stirred to dissolve the metal, and the temperature rises to 60°C. Add 20 ml of 1-pentanol and the solution is cooled to room temperature. Then add 24.8 g of 3-(3-methylpiperidino)phthalodinitrile and stirred for 8 hours under reflux at a temperature of 137°C. After cooling, the reaction mixture is filtered and the resulting filtrate concentrated. Get to 20.9 g of a phthalocyanine of the formula

in which PcLi2means tetravalent radical of a phthalocyanine, a Central element of which represents two times the lithium.

Conducted ultraviolet spectrometry in toluene at a concentration of 0.5 g/l:

max [nm]the extinctionthe extinction coefficient [l/cm·d]
772,00,858317,1660
716,00,9450 18,9000
332,00,763715,2740
300,00,762415,2480

Similarly, you can get the others listed in table 1 phthalocyanines.

1. Phthalocyanines of General formula I

in which Me means twice lithium, AlCl, AlOH, AlOCOCF3or SiCl2;

four of the radicals R1to R16denote independently from each other nitrogen-containing heterocyclic radical, which is substituted one or more times With1-C4-alkyl, benzyl, ventilation or phenyl and through a ring nitrogen atom is linked to the skeleton (skeleton) phthalocyanine and is a remnant of pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isoxazolidine, piperidine, piperazine, research or thiomorpholine, and

the other radicals R1to R16mean hydrogen.

2. Phthalocyanines according to claim 1, characterized in that they correspond to the formula Ia or IB

in which the radicals R4, R8, R12and R16and R2, R6, R10and R14mean each heterocyclic radical and Me is visiprise the military value, as well as their isomers provisions of the radicals R4, R8, R12and R16a R2, R6, R10and R14.

3. Phthalocyanines according to claim 1 or 2 as a means of marking mineral oils.



 

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SUBSTANCE: the invention is pertaining to the field of oil processing industry and motor-car industry, in particular, to the composition of the additive used in the automobile internal-combustion engines. The additive for the for the gasolines contains 15-30 % of N-methylaniline, 0.5-5.0 % of acetaldehyde, 0.01-1.0 % of a metalloorganic compound, 1.0-1.5 % of the hydrocarbon fraction boiling-off in the temperature interval of 60-200°C and ethyl alcohol - up to 100 %. As metalloorganic compound the additive can contain ferric dicyclopentadienyl, ferrocene and-or alfahydroxyisopropylferrocene, manganese cyclopentadienyltricarbonyl or its methyl derivative, molybdenum hexacarbonyl. The additive also can contain an antioxidant in amount of 1.0-1.5 mass % and-or up to 6 mass % of a washing additive. The invention ensures, that usage of the offered additive will allow to raise production of the high quality commercial gasolines for automobile engines, which shall provide purity of the automobile engines fuel system and the gasolines saving.

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3 cl, 1 tbl

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