DE4422336A1 - Use of leukotriarylmethanes for marking hydrocarbons - 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

The present invention relates to the use of leuko triarylmethanes of the formula I.

in the
Z optionally substituted phenyl, optionally substituted naphthyl or a radical of the formula

wherein
Y represents C₁-C₁₆ alkyl, and
R¹, R², R³ and R⁴ are the same or different and each independently represent hydrogen, C₁-C₁₆-alkyl which can be interrupted by 1 to 4 oxygen atoms in ether function and is optionally substituted, optionally substituted phenyl or optionally substituted naphthyl,
as a marking agent for hydrocarbons, hydrocarbons containing the above-mentioned leukotriarylmethanes, and a method for the detection of leukotriarylmethanes in hydrocarbons.

The object of the present invention was to develop new means for Provide marking hydrocarbons. The new Means should be easily accessible and in hydrocarbons  be soluble. They should also follow up in a simple manner can be pointed. Even very small ones Amounts of marking material visible through a strong color reaction can be made.

Accordingly, it was found that the above described themselves Leukotriarylmethanes of formula I advantageous as a marker suitable for hydrocarbons.

All alkyl radicals occurring in the above formula I can be both straight and branched.

If in the above formula I substituted phenyl or Naphthyl residues occur, they usually have 1 to 3 substituents.

If Z is substituted phenyl or naphthyl, then as substituents e.g. B. C₁-C₁₆ alkyl, C₁-C₁₆ alkoxy, halogen, amino or C₁-C₁₆ mono- or dialkylamino come into consideration.

When R¹, R², R³ or R⁴ substituted phenyl or substituted Naphthyl mean, such as substituents such. B. C₁-C₁₆ alkyl, that is interrupted by 1 to 4 oxygen atoms in ether function can be C₁-C₁₆ alkoxy or phenoxy.

If R¹, R², R³ and R⁴ are substituted C₁-C₁₆ alkyl, so can as substituents such. B. hydroxy, halogen or cyano in Come into consideration. The alkyl radicals then usually have 1 or 2 substituents.

R¹, R², R³, R⁴ and Y are, for. B. methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, Neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, Undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, Isotri decyl, tetradecyl, pentadecyl or hexadecyl (the above designations Solutions Isooctyl, Isononyl, Isodecyl and Isotridecyl are trivial designations and derive from those obtained after oxo synthesis Alcohols - cf. also Ullmann’s Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A1, pages 290 to 293, as well Vol. A10, pages 284 and 285).

R¹, R², R³ and R⁴ are still z. B. 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl,  3,6-dioxyoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxa decyl, 4,7-dioxaundecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 4,7,10-trioxaundecyl, 3,6,9,12-tetraoxa tridecyl, 3,6,9,12-tetraoxatetradecyl, 2-hydroxyethyl, 2-chlorine ethyl, 2-cyanoethyl, 2- or 3-hydroxypropyl, 2- or 3-chlorine propyl, 2- or 3-cyanopropyl, 2- or 4-hydroxybutyl, 2- or 4-chlorobutyl, 2- or 4-cyanobutyl, 5-hydroxypentyl, 5-chlorine pentyl, 5-cyanopentyl, 6-hydroxyhexyl, 5-chlorhexyl or 6-cyano hexyl.

Suitable substituents for the radical Z are, in addition to those already mentioned C₁-C₁₆ alkyl radicals, for. B. fluorine, chlorine, bromine, mono- or Dimethylamino, mono- or diethylamino, mono- or dipropylamino, Mono- or diisopropylamino, mono- or dibutylamino, mono- or Dipentylamino, mono- or dihexylamino, mono- or diheptylamino, Mono- or dioctylamino, mono- or bis (2-ethylhexyl) amino, mono- or dinonylamino, mono- or didecylamino, mono- or diundecyl amino, mono- or didodecylamino, mono- or ditridecylamino, Mono- or ditetradecylamino, mono- or dipentadecylamino, mono- or dihexadecylamino, N-methyl-N-ethylamino, methoxy, ethoxy, Propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, Isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy, 2-methyl pentyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, isooctyloxy, Nonyloxy, isononyloxy, decyloxy, isodecyloxy, undecyloxy, Dodecyloxy, tridecyloxy, 3,5,5,7-tetramethylnonyloxy, iso tridecyloxy, tetradecyloxy, pentadecyloxy or hexadecyloxy.

Leukotriarylmethanes of the formula I are preferred, in which Z is counter also substituted phenyl means for labeling Koh Hydrogen oils used.

Leukotriarylmethanes of the formula I are also preferred, in which R¹, R², R³, R⁴ are each independently C₁-C₆ alkyl mean used for marking hydrocarbons.

Leukotriarylmethanes of the formula II are particularly preferred

in which X is hydrogen, amino or C₁-C₄ mono- or dialkylamino means and R¹, R², R³ and R⁴ each have the meaning given above own, used for marking mineral oils.

Leukotriarylmethanes are very particularly preferred Formula II, in which X is hydrogen or C₁-C₆ dialkylamino, ins special dimethylamino, and R¹, R², R³ and R⁴ independently of one another are each other C₁-C₁₆ alkyl, especially methyl, used to mark hydrocarbons.

The leukotriarylmethanes of the formula I are known per se and e.g. B. in K. Vemkataraman "The Chemistry of Synthetic Dyes", Vol. II, Academic Press, New York, 1952 e.g. B. can be obtained by the methods mentioned there.

In the leukotriarylmethane of formula II with X = hydrogen and R¹, R², R³ and R⁴ = methyl, it is leukomalachite green, in those with X = dimethylamino and R¹, R², R³ and R⁴ = Methyl to leuco crystal violet.

Under marking in the sense of the invention is an addition of Leukotriarylmethanes of formula I in such a concentration Hydrocarbons to understand that the hydrocarbons thereby either not at all for the human eye or are only slightly visible, but the leukotriaryl methanes of the formula I by the detection described in more detail here methods are easily and clearly visible.

Another object of the present invention are coals Hydrogen containing one or more of the leukotriaryl methanes of formula I.

Among hydrocarbons in the sense of the invention are ali to understand phatic or aromatic hydrocarbons that are in a liquid state under normal conditions, e.g. B. pentane, hexane, heptane, octane, isooctane, benzene, toluene, Xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, chlorine benzene or dichlorobenzene. In particular, these are mineral oils, for example fuels, such as gasoline, kerosene or diesel oil, or oils such as heating oil or motor oil.

The leukotriarylmethanes of formula I are particularly suitable for Marking of mineral oils where marking is required will, e.g. B. for tax reasons. To the cost of the label The aim is to keep the voltage low, for the marking use the smallest possible amount of marker.  

To mark hydrocarbons, leukotriaryl methanes of formula I either in substance or in the form of Solutions applied. Organic solvents are suitable Solvent. Aromatic hydrocarbons are preferred substances such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatics, which is called Shellsol® AB (Shell) is commercially available. To a high One chooses to avoid viscosity of the resulting solutions generally a concentration of leukotriarylmethane I of 20 to 80 wt .-%, based on the solution.

Others can also be used to improve solubility Cosolvents, e.g. B. alcohols, such as methanol, ethanol, propanol, Isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, Octanol, 2-ethylhexanol or cyclohexanol, glycols, such as butyl ethylene glycol or methyl propylene 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 p-cresol, Ketones such as diethyl ketone or cyclohexanone, lactams such as γ-butyro lactone, carbonates, such as ethylene carbonate or propylene carbonate, Phenols, such as t-butylphenol or nonylphenol, esters, such as phthal Acid methyl ester, phthalic acid ethyl ester, phthalic acid (2-ethyl hexyl) ester, ethyl acetate, butyl acetate or Cyclohexyl acetate, amides, such as N, N-dimethylformamide, N, N- Diethylacetamide or N-methylpyrrolidinone, or their mixtures be used.

By means of the leukotriarylmethanes to be used according to the invention Formula I succeeds very easily, labeled hydrocarbons to be detected, even if the labeling substances only exist in one Concentration of about 10 ppm or less.

In some cases it is also advantageous to use mixtures of Leuko triarylmethanes of formula I with each other as a label to use substances.

Evidence of the presence of the as marking substances used leukotriarylmethanes of formula I in hydrocarbons succeeds advantageously if you have the labeled hydrocarbon with an oxidizing agent and optionally a protonic acid treated in the presence of water.

This treatment results in a clearly visible color reaction and the leukotriarylmethane I occurs with the formation of a Triarylmethane dye into the aqueous phase.  

The resulting triarylmethane dye obeys the Formula III

in which the Z, R¹, R², R³ and R⁴ each have the meaning given above and An⊖ means the equivalent of an anion (e.g. Sulfate, hydrogen sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, nitrate, acetate, lactate or citrate).

Suitable oxidizing agents are, for example, conventional ones known inorganic or organic oxidizing agents, such as alkali permanganates, e.g. B. potassium permanganate, ammonium dichromate, alkali dichromates, e.g. B. sodium or potassium dichromate, Ammonium peroxodisulfate, alkali peroxodisulfates such as sodium or Potassium peroxodisulfate, potassium peroxomonosulfate, iron (III) salts, e.g. B. iron (III) chloride or iron (III) sulfate, hydrogen peroxide (in combination with suitable catalysts), quinones, e.g. B. 2,3-dichloro-5,6-dicyanobenzoquinone or 2,3,5,6-tetrachlorobenzo quinone, sodium perborate or cerium (IV) salts, e.g. B. Cerium (IV) sulfate.

Depending on the type of oxidant, these can either as an aqueous solution (inorganic oxidizing agent) or as Solution in an organic solvent (organic oxidation medium) are used. Suitable organic solution means are z. B. toluene, xylene, cyclohexanone, acetophenone, γ-butyrolactone, 2-ethylhexyl acetate or ester or phthalic acid.

Works when using organic oxidizing agents one in the presence of a dilute aqueous acid, e.g. B. 5 to 30% by weight aqueous acetic acid. Even the application of the inorganic oxidizing agents can in the presence of acid, e.g. B. sulfuric acid.

The concentration of the oxidizing agent in the aqueous or organic solution is usually 0.001 to 5% by weight, preferably 0.01 to 1 wt .-%, each based on the weight the solution.  

The amount of acid can when using the aqueous solutions inorganic oxidizing agents in small amounts, e.g. B. some Drops, stay confined.

When using organic oxidizing agents, the amount is the acid used, e.g. 5 to 30 wt .-% aqueous acetic acid larger because the water contained in the acid as an aqueous phase serves. In this case it is advisable to add the amount of water To choose acid so that it is about the amount of too low searching hydrocarbon.

It is usually sufficient to use an amount of approximately 1 to 5 ml of the hydrocarbon labeled according to the invention with 2 to 10 ml a solution of an organic oxidizing agent in an organic rule solvent and 1 to 5 ml of aqueous acid or with 1 to 5 ml of an aqueous solution of an inorganic oxidizing agent, optionally in the presence of an acid, at a temperature of 10 to 100 ° C, preferably 20 to 80 ° C, to treat the color to get reaction. The treatment is advantageously carried out by shaking the hydrocarbon phase with the aqueous Phase.

The leukotriarylmethanes used according to the invention are easily accessible and readily soluble in hydrocarbons. They can also be detected in a simple manner, whereby even very small amounts of marking material due to a strong one Color reaction can be made visible.

The following examples are intended to explain the invention in more detail.

example 1

2 ml of a solution of 10 ppm leuco crystal violet in xylene were with 3.5 ml of a solution of 50 ppm 2,3-dichloro-5,6-dicyanobenzo quinone in xylene and after one minute with 2 ml Shake 20% by weight acetic acid until the dye is full was constantly dissolved in the aqueous phase. The aqueous phase shows an intense purple color.

Example 2

2 ml of a solution of 10 ppm leukomalachite green in xylene were with 3.5 ml of a solution of 50 ppm 2,3-dichloro-5,6-dicyanobenzo quinone in xylene and after one minute with 2 ml Shake 20% by weight acetic acid until the dye is full was constantly dissolved in the aqueous phase. The aqueous phase shows an intense green color.  

Example 3

2 ml of a solution of 10 ppm leuco crystal violet in commercial Conventional diesel fuel was mixed with 3.5 ml of 0.05% by weight Solution of 2,3-dichloro-5,6-dicyanobenzoquinone in xylene added and after one minute with 2 ml of 20% by weight acetic acid shaken until the dye is completely in the aqueous phase was solved. The aqueous phase shows an intense purple Coloring.

Example 4

2 ml of a solution of 10 ppm leukomalachite green in commercially available Diesel fuel was mixed with 3.5 ml of a 0.05 wt% solution of 2,3-dichloro-5,6-dicyanobenzoquinone in xylene and after one minute with 2 ml of 20% by weight acetic acid shaken until the dye is completely in the aqueous phase was solved. The aqueous phase shows an intense green color.

Example 5

2 ml of a 0.1% by weight solution of leuco crystal violet in Toluene was mixed with 1.5 ml of 0.1% by weight aqueous iron (III) chloride solution shaken for 15 sec and warmed to 70 ° C. It is to see a clear blue-violet color of the aqueous phase.

Example 6

2 ml of a 0.1% by weight solution of leuco crystal violet in Toluene was mixed with 1.5 ml of 0.1% by weight aqueous sodium peroxodi shaken sulfate solution for 15 sec and heated to 70 ° C. It is one clear blue-violet coloration of the aqueous phase can be seen.

Example 7

2 ml of a 0.1% by weight solution of leuco crystal violet in Toluene was mixed with 1.5 ml of 0.1% by weight aqueous potassium per manganate solution and 2 drops of 10% by weight sulfuric acid for 15 sec shaken. The intrinsic color of the potassium permanganate decreased and a distinct blue-violet appeared in the aqueous phase Coloring on.  

Example 8

2 ml of a 0.1% by weight solution of leuco crystal violet in Toluene, 1.5 ml 0.1 wt .-% aqueous potassium permanganate solution and 2 drops of 10% by weight sulfuric acid were shaken for 15 seconds and heated to 70 ° C. It is a clear blue-violet color to see the aqueous phase.

Claims (6)

1. Use of leukotriarylmethanes of the formula I in the
Z optionally substituted phenyl, optionally substituted naphthyl or a radical of the formula Y represents C₁-C₁₆ alkyl, and
R¹, R², R³ and R⁴ are the same or different and are each independently hydrogen, C₁-C₁₆-alkyl which can be interrupted by 1 to 4 oxygen atoms in ether function and is optionally substituted, optionally substituted phenyl or optionally substituted naphthyl,
as a marking agent for hydrocarbons. 2. Use of leukotriarylmethanes according to claim 1, characterized characterized in that Z is optionally substituted phenyl means. 3. Use of leukotriarylmethanes according to claim 1, characterized characterized in that R¹, R², R³, R⁴ independently of one another are each C₁-C₆ alkyl.   4. Use of leukotriarylmethanes according to claim 1, which of the formula II obey in which X is hydrogen, amino or C₁-C₁₆ mono- or dialkylamino and R¹, R², R³ and R⁴ each have the meaning given in claim 1. 5. hydrocarbons containing as a marking agent one or more leukotriarylmethanes of the formula I according to Claim 1. 6. Method for detecting the presence of leukotriaryl methanes of formula I according to claim 1 in hydrocarbon fabrics, characterized in that the marked Hydrocarbon with an oxidizing agent and given if treated with a protonic acid in the presence of water.