CZ381196A3 - Use of leukotriaryl methane for labelling hydrocarbons, method of its detection in the hydrocarbons and the hydrocarbons containing thereof - Google Patents

Abstract

The invention concerns the use, as markers for hydrocarbons, of leucotriarylmethanes of formula (I) in which Z is an aromatic carbocyclic or heterocyclic group and R<1>, R<2>, R<3> and R<4> are hydrogen, optionally substituted C1-C16 alkyl, optionally substituted phenyl or optionally substituted naphthyl. The invention also concerns hydrocarbons containing such leucotriarylmethanes and a method of detecting leucotriarylmethanes in hydrocarbons.

Description

Technical field? i: f / 5 I o • f-0 «muiih.

The invention relates to the use of leukotriarylmethane derivatives for the labeling of hydrocarbons, to a method for demonstrating the presence of a leukotriarylmethane derivative in hydrocarbons and to hydrocarbons containing a leukotriarylmethane derivative.

BACKGROUND OF THE INVENTION

Various agents are already known from the literature and are used as mineral oil markers. The marking of mineral oils is important for taxation reasons. At the same time, it is desirable that the cost of marking is minimal, it is sought to ensure that only a minimum amount of the marking agent is used for the marking.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel means for marking hydrocarbons. The new composition should be readily available and well soluble in hydrocarbons. In addition, it should be easy to prove. Such a composition should also be visible in small amounts by a strong staining reaction.

Surprisingly, it has been found that the leukotriarylmethane derivatives of the formula I are preferably suitable for the labeling of hydrocarbons.

SUMMARY OF THE INVENTION

The present invention relates to the use of the leukotriarylmethane derivatives of the formula I

R ¹ z

R ²

N.

where it means

Z is optionally substituted phenyl, optionally substituted naphthyl or a group of the formula

* N

AND

Y wherein Y is C 1 -C 16 alkyl and R ¹ , R ² , R ³ and R ⁴ are independently hydrogen, C 1 -C 16 alkyl optionally interrupted by C 1 -C 4 oxygen atoms function and is an optionally substituted and optionally substituted phenyl or optionally substituted naphthyl group to label hydrocarbons.

The present invention also relates to hydrocarbons containing leukotriarylmethane derivatives and to a method for the detection of leukotriarylmethane derivatives in hydrocarbons.

All alkyl groups occurring in the above formulas may be both straight chain and branched.

When substituted phenyl or naphthyl groups are present in these formulas, they generally have 1 to 3 substituents.

If Z is a substituted phenyl or naphthyl group, suitable substituents are, for example, C1-C16-alkyl and C1-C16-alkoxy, halogen, umino or monoalkyl-C1-C16-alkoxy. Or C 1 -C 16 dialkylamino.

When R @ ^1, R @ ² , R @ ³ and R @ ^{4 are a} substituted phenyl or a substituted naphthyl group, an alkyl group having from 1 to 16 carbon atoms, optionally interrupted by 1 to 4 oxygen atoms in the ether function, alkoxy to 1 to 16 carbon atoms, or phenoxy.

When R @ ^1, R @ ² , R @ ³ and R @ ^{4 are} substituted alkyl having from 1 to 16 carbon atoms, suitable substituents are, for example, hydroxy, halogen or cyano. The alkyl groups then typically have one or two substituents.

R ¹ , R ² , R ³ , R ⁴ and Y are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylphenyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl, tetradecyl, pentadecyl or hexadecyl, isodecyl, and isotridecyl are trivial designations and are derived from alcohols prepared by oxosynthesis (Ullman ' s Encyclopedia of Industrial Chemistry, 5th Edition, Volume A1, pages 290-293 and Volume A10 pages 284-285).

R ^{@ 1} , R ^{@ 2} , R ^{@ 3} and R ^{@ 4} are furthermore, for example, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2-methoxypropyl or 3methoxypropyl, 2-ethoxypropyl or 3-ethoxypropyl, 2propoxypropyl; 3-propoxypropyl, 2-butoxypropyl or 3-butoxypropyl, 2-methoxybutyl or 4-methoxybutyl, 2-ethoxybutyl or 4-ethoxybutyl, 2-propoxybutyl or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4, 8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2-butoxybutyl or 4-butoxybutyl, 4,8-dioxadecyl, 4,7-dioxaundecyl, 3,6, 9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6, 9-trioxadodecyl, 4,7,10-trioxaundecyl, 3,6, 9,12-tetraoxatridecyl,

3,6,9,12-tetraoxatetradecyl, 2-hydroxyethyl, 2-chloroethyl, 2-cyanoethyl, 2-hydroxypropyl or 3-hydroxypropyl, 2-chloropropyl or 3-chloropropyl, 2-cyanopropyl or 3-cyanopropyl, 2-hydroxybutyl or 4-hydroxybutyl, 2-chlorobutyl or 4-chlorobutyl, 2-cyanobutyl or 4-cyanobutyl, 5-hydroxypentyl, 5-chloropentyl, 5-cyanpentyl, 6-hydroxyhexyl, 6-chlorhexyl or 6-cyanhexyl.

In addition to said C 1 -C 16 alkyl groups, suitable substituents for Z are, for example, fluorine, chlorine, bromine, monomethylamino or dimethylamino, monoethylamino or diethylamino, monopropylamino or dipropylamino, monoisopropylamino or diisopropylamino, diisopropylamino or diisopropylamino; dihexylamino, monoheptylaminoskupina or diheptylaminoskupina, monooktylaminoskupina or dioctylamino, mono (2-ethylhexyl) amino or di (2ethylhexy1) amino, monononylaminoskupina or dinonylaminoskupina, monodecylaminoskupina or didecylaminoskupina, monoundecylaminoskupina or diundecylaminoskupina, monododecylaminoskupina or didodecylaminoskupina, monotridecylaminoskupina or ditridecylaminoskupina, monotetradecylaminoskupina or ditetra, decylaminoskupina, monopentadecylarainoskup INA or dipentadecylaminoskupina, monohexadecylaminoskupina dihexadecylaminoskupina or N-methyl-N-ethylamino, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxyskupi5 on, s'ek.-butoxy, pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy, 2metylpentyloxyskupina , heptyloxyskup on, o.ktyloxyskup on, 2-ethylhexyloxy, isooctyloxy, nonyloxy, isononyloxyskupina, decyloxy, isodecyloxyskupina, undecyloxyskupina, dodecyloxy, tridecyloxyskupina, .3,5,5,7-tetramethylnonyloxyskupina isotridecyloxyskupina, tetradecyloxy, or pentadecyloxysk'upina ' hexadecyloxy.

Preferred are the leukotriarylmethane derivatives of formula I, wherein Z is an optionally substituted phenyl group for the labeling of hydrocarbons.

Furthermore preferred are derivatives of the triarylmethanes of the formula I wherein R ^1, R ^2, R ³ and R ⁴ are independently alkyl having 1 to 6 carbon atoms, for marking hydrocarbons.

Particularly preferred are the leukotriarylmethane derivatives of the general formula II.

wherein X is hydrogen, amino, C 1 -C 16 monoalkylamino or C 1 -C 16 dialkylamino and R ^1, R ² _, R ^3, _and R ⁴ are as defined above to indicate hydrocarbons.

Particularly preferred are the leukotriarylmethane derivatives of the formula (II) in which X represents a hydrogen atom or a C1 -C1 dialkylamino group, in particular a dimethylamino group and R @ ¹ , R @ ² , R @ ³ and R ^{@ 4} independently of one another. carbon, especially methyl, to label a hydrocarbon.

The leukotriarylmethane derivatives of the formula I are known per se and are described, for example, in The Chemistry of Synthetic Dyes, K. Venkataraman, Vol. II, Academic Press, New York, 1952, and can be prepared by the methods described therein.

For derivatives triarylmethanes of the formula II where X is hydrogen and R ^1, R ^2, R ³ and R ⁴ each represents a methyl, regards 1eukomalachi isethionate vegetation and in the case where X represents dimethylamino, and R ^1, R ^2, R ³ and R ^{4 is} each methyl, it is a leucocrystalline violet.

The term hydrocarbon marking according to the invention means the addition of the leukotriarylmethane derivatives of the formula I to the hydrocarbons in such an amount that the hydrocarbons become imperceptible or only slightly visible to the human eye, but the leukotriarylmethane derivatives of the formula I are clearly described below provable.

The invention further relates to hydrocarbons containing one or more leukotriarylmethane derivatives of the general formula I. The concentration of the leukotriarylmethane derivatives of the general formula I in hydrocarbons is generally from 1 to 500 ppm, preferably from 5 to 50 ppm and in particular approximately 40 ppm.

The term hydrocarbons refers to aliphatic or aromatic hydrocarbons which are normally in the liquid state, for example pentane, hexane, heptane, octane, isooctane, benzene, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthaline, diisopropylnaphthaline, chlorobenzene or dichlorobenzene. In particular, they are mineral oils, for example fuels such as gasoline, kerosene or diesel or oils such as fuel oils or engine oils.

The leukotriarylmethane derivatives of the formula I are particularly suitable for marking mineral oils for which marking is required, for example for taxation reasons. In order to make the cost of the marking noticeable, it is sought to use only a minimum amount of the marking agent for the marking.

The leukotriarylmethane derivatives of the formula I are used either as such or in the form of solutions for the labeling of hydrocarbons. Suitable solvents are organic solvents. Aromatic hydrocarbons such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatic substances under the trade name Shellsol ^R AB (Shell) are suitable. In order to avoid the high viscosity of the solutions obtained, the weight concentration of the leukotriarylmethane derivatives of the formula I is generally chosen to be 20 to 80%, based on the solution as a whole.

Other cosolvents may be used to improve solubility. Examples are alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol and cyclohexanol; glycols such as butylethylene glycol or methylpropylene glycol; amines such as triethylamine, diisooctylamine, dicyclohexylamine, aniline, N-methylaniline, N, N-dimethylaniline, toluidine or xylidine; alkanolamines such as 3- (2-methoxyethoxy) propylamine; o-cresol, m-cresol or cresol; ketones such as diethylketone or cyclohexanone; lactams such as gamma butyrolactone; carbonates such as ethylene carbonate or propylene carbonate; phenols such as tert-butylphenol or nonylphenol; esters such as phthalic acid methyl ester, phthalic acid ethyl ester, phthalic acid 2-ethylhexyl ester, ethyl acetate, butyl acetate or cyclohexyl acetate; amides such as N, N-dimethylformamide, N, N-diethylacetamide or N-methylpyrrolidone or mixtures thereof.

By using the leukotriarylmethane derivatives of the formula I according to the invention, it is very easy to detect the labeled hydrocarbons even if the label is only in a concentration of approximately 10 ppm or even lower.

In many cases, it is advantageous to use mixtures of the leukotriarylmethane derivatives of the general formula I as a marking agent.

The detection of the presence of the leukotriarylmethane derivatives of the general formula (I) used as hydrocarbons in the hydrocarbons is preferably carried out by treating the labeled hydrocarbon with an oxidizing agent and optionally with protonic acid in the presence of water. In this treatment, a markedly visible color reaction occurs and the leukotriarylmethane derivative of formula I passes into the aqueous phase to form a triarylmethane dye.

The resulting ^- triarylmethane dye has the general formula III

Rl

R ²

An (III) wherein Z, R, R ^2, R ³ and R ⁴ are each as defined above and n 'is one equivalent of an anion (for example, a group of sulfate, bisulfate, phosphate, hydrogen phosphate, dihydrogenphosphate, nitrate, acetate, lactate or citrate) .

Suitable oxidizing agents include, for example, customary inorganic or organic oxidizing agents known per se, such as, for example, alkaline permanganates such as potassium permanganate, ammonium dichromate, alkaline dichromates, such as sodium or potassium dichromate, ammonium peroxodisulfate, alkaline proxodisulfates such as sodium peroxodisulfate or sodium peroxodisulfate. potassium peroxomonosulfate, ferric salts such as ferric chloride or sulfate, hydrogen peroxide (in combination with suitable catalysts) quinones such as 2,3-dichloro-5,6-dicyanobenzoquinone or 2,3,5,6-tetrachlorobenzoquinone, sodium perborate or cerium salts, as cerium sulphate.

Depending on the nature, oxidizing agents can be used either as aqueous solutions (inorganic oxidizing agents) or as solutions in organic solvents (organic oxidizing agents). Suitable organic solvents are, for example, tolene, xylene, cyclohexanone, acetophenone, gamma-butyrolactone, 2-ethyl acetate or phthalic acid ester.

When organic oxidizing agents are used, the reaction is carried out in the presence of a dilute aqueous acid, for example 5 to 30% acetic acid. Inorganic oxidizing agents can also be used in the presence of acids such as sulfuric acid.

The amount of oxidizing agent by weight in the aqueous or organic solvent is generally 0.001 to 5%, preferably 0.01 to 1%, based on the total weight of the solution.

In the case of aqueous solutions of inorganic oxidizing agents, the amount of acid is limited to a small amount, for example a few drops.

When organic oxidizing agents are used, the amount of acid used, for example 5 to 30% aqueous acetic acid, is greater, since the water contained in the acid serves as the aqueous phase. In this case, it is recommended to select the amount of aqueous acid to be approximately equal to the amount of hydrocarbon under investigation.

In general, an amount of about 1 to 5 ml of the inventive labeled hydrocarbon with 2 to 10 ml of an organic oxidizing agent solution in an organic solvent and 1 to 5 ml of an aqueous acid or 1 to 5 ml of an aqueous solution of an inorganic oxidizing agent is optionally sufficient in the presence of acid at 10 to 100. ° C, preferably 20 to 80 ° C to achieve a color reaction. Preferably, the proof is performed by shaking the hydrocarbon phase with the aqueous phase.

The leukotriarylmethane derivatives of the formula (I) which are used according to the invention are readily available and are readily soluble in hydrocarbons. In addition, they are detectable in a simple manner, and even a very small amount of the marker is visible by a strong stained reaction.

The invention is illustrated, but not limited, by the following examples. Percentages and parts are by weight unless otherwise stated.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Mix 2 ml of a 10 ppm leucocrystalline violet solution in xylene with 3.5 ml of a 50 ppm solution of 2,3-dichloro-5,6-dicyclobenzoquino in xylene and shake for one minute with 2 ml of 2 acetic acid until the dye dissolves perfectly in the aqueous phase The aqueous phase shows an intense violet coloration.

ynu

0%.

Example 2

Mix 2 ml of a 10 ppm leucomalachite green solution in xylene with 3.5 ml of a 50 ppm solution of 2,3-dichloro-5,6-dicyclobenzoquinone in xylene and shake for one minute with 2 ml of 20% acetic acid until the dye dissolves perfectly in the aqueous phase: The aqueous phase shows an intense green color.

Example 3

Mix 2 ml of a 10 ppm leucocrystalline violet solution in commercial diesel with 3.5 ml of a 0.05% solution of 2,3-dichloro

Shake 5,6-dicyclobenzoquinone in xylene and after 1 minute with 2 ml of 20% acetic acid until the dye is completely dissolved in the aqueous phase. The aqueous phase shows intense violet coloring.

Example 4

Mix 2 ml of a 10 ppm leucomalachite green solution in commercial diesel with 3.5 ml of a 0.05% solution of a 2,3% dichloro-5,6-dicyclobenzoquinone in xylene and shake for one minute with 2 ml of 20% acetic acid. until the dye is completely dissolved in the aqueous phase. The aqueous phase shows an intense green color.

Example 5

Shake 2 ml of a 0,1% solution of leucocrystalline violet in toluene with 1,5 ml of a solution of 0,1% aqueous ferric chloride solution for 15 seconds and heat to 70 ° C. The aqueous phase shows a strong blue-violet coloration.

Example 6

Shake 2 ml of a 0,1% solution of leucocrystalline violet in toluene with 1,5 ml of a 0,1% aqueous solution of sodium peroxodisulphate for 15 seconds and heat to 70 ° C. The aqueous phase shows a strong blue-violet coloration.

Example 7

Shake 2 ml of a 0,1% solution of leucocrystalline violet in toluene with 1,5 ml of a solution of 0,1% aqueous potassium permanganate with two drops of 10% sulfuric acid for 15 seconds. The color of the potassium permanganate itself recedes and the aqueous phase shows a distinctive blue-violet coloration.

Example 8

Shake 2 ml of a 0,1% solution of leucocrystalline violet in toluene with 1,5 ml of a solution of 0,1% aqueous potassium permanganate with two drops of 10% sulfuric acid for 15 seconds and heat to 70 ° C. The aqueous phase shows a strong blue-violet coloration.

Industrial applicability

Use of readily available, well soluble and readily even in small amounts by strong color reaction of a demonstrable leukotriarylmethane derivative to label a hydrocarbon.

Claims (6)

PATENTOVÉ ' Claims Use of a 1eukotriarylmethane derivative of the formula I R ² • over JAIOINÍSVIA ÓH3, \ msÁwgyd ₍ ανϋ o (I £ 6 ΟιξΟα í ' 7, 7: 1 where p is 0 Z is optionally substituted phenyl, optionally substituted naphthyl, or a group of the formula wherein is Y is C 1 -C 16 alkyl; R @ ¹ , R @ ² , R @ ³ and R ^{@ 4} independently of one another represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, optionally interrupted by 1 to 4 oxygen atoms in ether function and optionally substituted and optionally substituted phenyl or optionally substituted a naphthyl group to label the hydrocarbon. 2. The use according to claim 1 of the leukotriarylmethane derivative of the general formula I wherein Z is optionally substituted phenyl. sku - Use according to claim 1 of a leukotriarylmethane derivative of the general formula Ia, wherein R ¹ , R ² , R ² and R 3 are independently C 1 -C 6 alkyl. Use according to claim 1 of leukotriarylmethane derivatives of formula II ecR ¹ R ² (II) wherein X is hydrogen, amino well, monoalkylamino having 1 to 16 carbon atoms or dialkylamino having 1 to 16 carbon atoms in the alkyl group and R ^1, R ^2, R ³ and R ⁴ are ^as in claim 1, this meaning for the marking of hydrocarbons. 5. Hydrocarbons, characterized in that they contain at least one leukotriarylmethane derivative of the formula I as a marking agent according to claim 1. oe a 6. A method for detecting the presence of a leukotriarylmethane derivative of the formula I in hydrocarbons, characterized in that the labeled hydrocarbon is treated with an oxidizing agent or a protonic acid in the presence of water.