WO2007107569A1 - Markers for hydrocarbons - Google Patents

Abstract

A mixture comprising one or more hydrocarbons, a marker for the hydrocarbon(s) and preferably one or more further additives is described, where the marker comprises one or more compounds of the formula (I) or consists of one or more compounds of the formula (I), where R<SUP>1</SUP> is a branched or unbranched alkyl group having 1 to 6 C atoms, preferably a branched or unbranched alkyl group having 1 to 5 C atoms, particularly preferably an unbranched alkyl group having 1 to 3 C atoms and particularly preferably ethyl, R<SUP>2</SUP> is H or a branched or unbranched alkyl group having 1 to 6 C atoms, preferably H or a branched or unbranched alkyl group having 1 to 5 C atoms, particularly preferably an unbranched alkyl group having 1 to 3 C atoms, and particularly preferably methyl, and Y is CH<SUB>2</SUB>, CH-CH<SUB>3</SUB> or C=O, preferably CH<SUB>2</SUB> or C=O, particularly preferably C=O.

Description

Symrise GmbH & Co. KG Mühlenfeldstrasse 1, 37603 Holzminden

Marking agent for hydrocarbons

The present invention relates to the use of compounds of the formula (I) given below as (pH-dependent) marking agents for hydrocarbons, in particular for petroleum-derived fuels or lubricants (mineral oils). The invention further relates to corresponding mixtures comprising one or more hydrocarbons and the said marking agents. Moreover, the present invention relates to methods for labeling a hydrocarbon or a hydrocarbon mixture in which one or more compounds of the formula (I) are added as a marking agent to the hydrocarbon or the hydrocarbon mixture. Finally, the invention also relates to a process for the detection of compounds of the formula (I) in a mixture according to the invention under the action of an aqueous, acidic fuchsinschwefeligen solution (eg Schiff's reagent), wherein a visible color reaction occurs (identification of a labeled hydrocarbon or a marked hydrocarbon mixture). For various reasons, there is a need for marking hydrocarbons or hydrocarbon mixtures and especially mineral oil products. For example, in Germany diesel is taxed lower for agricultural use than for normal cars, so a corresponding marking is required. But also, for example, to distinguish high quality diesel over lower quality grades markers are added. There is often the desire to use a marking agent, the presence of the marked hydrocarbon or hydrocarbon mixture (ie, for example, a mineral oil product such as diesel) is not readily apparent; only after carrying out a preferably simple detection test should the mark become clearly recognizable.

1-Alkoxyesters have been described variously in the patent literature, they are e.g. used in the fragrance and flavor industry as depot preparations for the release of aldehydes (see US 4,296,137, US 4,386,063 and EP 1 285 906).

EP 0 385 441 describes the use of 1, 4-dimethyl-2-nitrobenzene as a marker for mineral oil products, in particular diesel. The lower detection limit is in the range of 20 to 100 ppm. The detection of the presence of the employed as a marker 1, 4-dimethyl-2-nitrobenzene succeeds via thin-layer chromatography and comprises several steps; he is thus consuming and feasible only in the laboratory. Furthermore, a semi-quantitative method using UV light is described, which is feasible only from a concentration of 100 ppm.

The use of (C 1 -C ₄ ) -alkyl phenyl ketones such as acetophenone as marker substances for mineral oil products and organic solvents is described in EP 0 310 319. The use concentration of the marker substance should therefore be in the range of 100 to 10,000 ppm and in particular 1000 ppm. The presence of the (CrC ₄ ) -Alkylphenylketone used as markers is achieved by a multi-step process, wherein Key component 2,4-dinitrophenylhydrazine is added, which leads to a clearly visible color reaction.

Aniline derivatives as marking agents for mineral oils are described in DE 42 38 994. The minimum detection concentration is 10 ppm or below. The presence of the aniline derivatives used as markers can be demonstrated by treating the labeled mineral oil with an aqueous acidic diazonium salt solution so that the aniline derivative couples with the diazonium salt to form an azo dye, ultimately resulting in a clearly visible color reaction. However, diazonium salts are not safe for safety and health reasons.

EP 0 736 080 describes azo dyes as pH-dependent marking agents for labeling hydrocarbons. The minimum detection concentration is 10 ppm or below. The presence of the azo dyes used as markers can be demonstrated by treating the labeled hydrocarbon with an acidic aqueous-alcoholic or acidic alcoholic solution which optionally also contains a metal halide. This results in a clearly visible color reaction.

The above acknowledged prior art discloses (a) readily available, but only consuming detectable markers and on the other hand (b) marking agents, although easy to detect, but their product properties make their handling consuming (such as crystalline state, see EP 0 736 080 and health concern, see DE 42 38 994).

In view of the above-referenced prior art, it has been the primary object of the present invention to provide alternative or improved means for marking hydrocarbons (especially hydrocarbon mixtures such as mineral oils, eg diesel). The marking agents should fulfill a number of requirements, in particular: easy accessibility

Usability even in concentrated form

Colorless good solubility in the hydrocarbon to be marked (mixture) - high stability in the hydrocarbon to be marked (mixture) inert behavior towards the hydrocarbons to be marked and optionally added additives preferably no occurrence in hydrocarbons obtained from natural sources, especially mineral oils - easy detectability in Mixtures with the hydrocarbons or hydrocarbon mixtures to be marked Detection of even small amounts of marking agents by pronounced color reaction Rapid progress of the detection reaction - poor removability from the hydrocarbon mixture.

According to a first aspect, the stated object is achieved by a mixture comprising

one or more hydrocarbons, a marking agent for the hydrocarbon (s), and preferably one or more further additives,

wherein the labeling agent comprises one or more compounds of the formula (I) or consists of one or more compounds of the formula (I)

(I)

in which R ^{1 is} a branched or unbranched alkyl group having 1 to 6 C atoms, preferably a branched or unbranched alkyl group having 1 to 5 C atoms, particularly preferably an unbranched alkyl group having 1 to 3 C atoms and especially preferably ethyl,

R ^{2 is} H or a branched or unbranched alkyl group having 1 to 6 C atoms, preferably H or a branched or unbranched alkyl group having 1 to 5 C atoms, more preferably an unbranched alkyl group having 1 to 3 C atoms, and particularly preferred Methyl, and

Y is CH ₂ , CH-CH ₃ or C = O, preferably CH ₂ or C = O, more preferably C = O.

Preferably, in the case of a mixture according to the invention, the proviso is: A mixture according to the invention in the form of a fuel comprising 1-ethoxyethyl acetate or 1-methoxyethyl acetate does not comprise any lead-containing anti-knock agent. With regard to fuels comprising a lead-containing anti-knock agent and 1-ethoxyethyl acetate or 1-methoxyethyl acetate to increase the octane number, reference is made to US 3,087,801.

Alternatively or additionally preferred is a mixture according to the invention for which the following applies: The mixture does not consist of 5-35% by weight of acetaldehyde diethyl acetal, 2-8% by weight of dibutyl ether, 10-35% by weight of alcohol and 22-83% by weight. % Kerosene or light oil (with regard to mixtures having the stated composition, see EP 1 149 887 A2).

Particularly preferred is a mixture according to the invention for which both provisos mentioned above apply simultaneously.

Very particular preference is given to a mixture for which the following applies: A mixture according to the invention in the form of a fuel comprising a compound of the

Formula (I) wherein Y is C = O does not include a lead-containing anti-knock agent. At the same Preferably, a mixture according to the invention comprising kerosene or light oil is preferably free from acetaldehyde diethyl acetal.

Particularly preferred is a mixture according to the invention, for which the following applies: The mixture does not comprise a lead-containing anti-knock agent. At the same time, preferably, a mixture comprising kerosene or light oil is free from acetaldehyde diethyl acetal.

In this case, any combination of a preferred meaning of one of the groups R ¹ , R ² or Y with one of the meanings of the other groups given is itself a preferred combination. Thus, for example, it is preferable to provide as R ^{1 group} an unbranched alkyl group having 1 to 2 C atoms, irrespective of whether R ² and / or Y themselves have a preferred meaning or not.

However, particular preference is given to mixtures according to the invention in which the marking agent comprises one or more compounds of the formula (I) or consists of one or more compounds of the formula (I)

R ^{1 is} a branched or unbranched alkyl group having 1 to 5 C atoms,

R ^{2 is} H or a branched or unbranched alkyl group having 1 to 5 C atoms and

Y is CH ₂ or C = O.

More preferred is a mixture according to the invention, wherein the marking agent comprises one or more compounds of formula (I) or consists of one or more compounds of formula (I), wherein

R ^{1 is} an unbranched alkyl group having 1 to 3 C atoms,

R ^{2 is} an unbranched alkyl group having 1 to 3 C atoms and YC = O means.

A use of compounds of the formula (I) as a marking agent is not known from the prior art. In US 3,087,801 leaded fuel is described containing 1, 1 -Etherester as an octane enhancer. EP 1 149 887 A2 describes low-emission fuels which comprise an additive containing oxygen atoms for increasing the combustibility. The present invention does not relate to mixtures as known from US 3,087,801 or EP 1 149 887 A2.

The marking agents to be used according to the invention, which comprise one or more compounds of the formula (I), meet all the requirements indicated above. They are very stable, especially in mineral oils, and the detection reaction with Schiff's reagent is very rapid and reliable. Because of the color reaction occurring in the detection with Schiff's reagent, photometric quantification of the compounds of the formula (I) is also possible. This allows, for example, to detect an undesirable dilution of an originally used hydrocarbon mixture (e.g., a mineral oil such as diesel).

Most preferred are mixtures according to the invention in which the marking agent comprises one or more compounds of the formula (I) or consists of one or more compounds of the formula (I), where in the compound of the formula (I) or in one of the compounds of Formula (I)

R ^{1 is} ethyl,

R ^{2 is} methyl and

Y C = O means.

Most preferred is thus the use of 1-ethoxyethyl acetate having the following structural formula (Ia) (formula (I) where R ¹ = ethyl; R ² = methyl; Y = C = O; CAS No .: 1608-72-6, for example, as described in US 4,387,036 and commercially available):

(Ia)

Particularly good results were obtained with 1-ethoxyethyl acetate as a marking agent, it shows excellent stability in hydrocarbons, in particular mineral oils, and the detection reaction with Schiff's reagent proceeds very rapidly and reliably.

The labeling agents of the formula (I) to be used according to the invention react under hydrolyzing action of an aqueous acid fuchsinschwefeligen acid solution (Schiff's reagent) to form acetaldehyde, which in turn enters into a color reaction with the fuchsinschwefeligen acid, i. it comes to a color change, along with a clearly visible color deepening.

The so-called Schiff's reagent (also: Schiff's reagent, fuchsin / sulfuric acid) is a detection agent for aldehydes introduced by H. Schiff. General Preparation Procedure for Schiff's Reagent: dissolve fuchsin in distilled water and decolorize after addition of hydrochloric acid with sodium sulfite (formation of sulfur dioxide). This colorless solution turns red with aldehyde addition; for the mechanism of reaction, see literature (e.g., Anal Chem 32, 1307-1311 (1960)).

Fuchsin (empirical formula: C ₂ OH ₁₉ N ₃ , M _R 301, 39) has the following structural formula [(methyl fuchsin, 3-methyl parafuchsin, 4 - [(4-aminophenyl) - (4-imino-2,5-cyclohexadiene-1 -ylidene) -methyl] -2-methylaniline, Basic Violet 14, CI 42510]

By aqueous acid fuchsinschwefeliger acid solution is a well-known in the art commercially available fuchsinschwefelige acid (Schiff's reagent) for the detection of aldehydes to understand. (e.g., Merck KGaA, 64271 Darmstadt, article number: 109034).

The mixtures according to the invention are present under normal conditions (1013 mbar, 25 ° C.) in the liquid state. They comprise one or more hydrocarbons, which are preferably straight-chain or branched-chain aliphatic or aromatic hydrocarbons, in particular hydrocarbons derived from petroleum. Usually, several different hydrocarbons are present in a mixture according to the invention, i. there is a hydrocarbon mixture. Preferred hydrocarbon mixtures present in a mixture according to the invention are mineral oils, i. energy sources (fuels, fuels) or lubricants (oils and fats) produced from petroleum (crude oil).

Hydrocarbon mixtures (comprising a plurality of hydrocarbons) which can be marked particularly preferably by the marking agents to be used according to the invention are, in particular, mineral oils (see above), in the context of the present invention mineral oils being fuels, in particular gasoline (in particular gasoline according to DIN EN 228), Kerosene (eg Aviation gasoline in accordance with ASTM D910 grade 100 LL or jet fuel, jet fuel such as Jet A-1 or Jet B) or diesel (in particular according to DIN EN 590) and oils, in particular fuel oil (in particular according to DIN 51603) or engine oil. Particular preference is again given to the so-called middle distillates, which have a boiling range of from 180 to 360 ° C. under atmospheric pressure (1013 mbar); diesel fuel according to DIN EN 590 is particularly preferred.

Commercially available fuels or oils, such as diesel fuels or heating oils, which are to be characterized in accordance with the invention using a marking agent, regularly contain additives. A mixture according to the invention therefore comprises (in particular if it comprises petroleum-derived fuels or lubricants which contain a plurality of hydrocarbons), preferably in a total concentration in the range from 0.0001 to 2% by volume, based on the total volume of the mixture, of one or more Additives selected from the group consisting of: flow improvers (flow improvers, anti-settling, eg diesel fuel wax anti-settling additives, WASA), oxidation inhibitors (antioxidants), metal deactivators, corrosion inhibitors, anti-foams, ignition accelerators, detergents, particle-reducing Substances, anti-knock agents, anti-carburetor additives, anti-repellency agents, anti-smoke agents, biocides, conductivity improvers, burn-off aids, fragrances, anti-wear agents and viscosity improvers. A petroleum-based lubricant may also be added to a mixture according to the invention comprising a petroleum-derived fuel.

For the preparation of a mixture according to the invention, it may be helpful for ease of dosing or handling, the marking agent one or more hydrocarbons (eg, a mineral oil such as a middle distillate (eg diesel)) in the form of a mixture with one or more solution or Add diluents. The solvent or diluents must be compatible with the marking agent (s) and the hydrocarbons to be marked. Preferred solvents or diluents are substances from one of the following groups L1 and L2 or a mixture of substances from both groups L1 and L2, consisting of:

(L1) isopropyl myristate, benzyl benzoate, diethyl phthalate and mixtures thereof,

(L2) isododecane, n-paraffins having 9 to 14 carbon atoms, iso-paraffins having 9 to 14 carbon atoms, naphthalene, alkylnaphthalenes (especially methylnaphthalenes) and mixtures thereof.

The invention also relates to a corresponding mixture comprising marking agents and a solvent or diluent compatible therewith (and preferably with the hydrocarbons to be marked). Such a mixture according to the invention preferably comprises

based on the total weight of the mixture 40 to 95 wt .-%, preferably 50 to 90 wt .-% of one or more compounds of formula (I)

(I)

wherein R ¹ , R ² and Y have the meaning given in claims 1 to 4,

such as

a substance from one of the following groups L1 and L2 or a mixture of substances from both groups L1 and L2, consisting of:

(L1) isopropyl myristate, benzyl benzoate, diethyl phthalate and mixtures thereof, (L2) isododecane, n-paraffins having 9 to 14 carbon atoms, iso-paraffins having 9 to 14 carbon atoms, naphthalene, alkylnaphthalenes (especially methylnaphthalenes) and mixtures thereof.

Preferably apply to a "mixture comprising marking agent according to the invention and a solution or. Diluent "the abovementioned provisos, which apply to a" mixture comprising one or more hydrocarbons and a marking agent "according to the invention, according to.

Solvents of the group L2 are e.g. under the name Shellsol D60 or Shellsol D100 (mixtures of n- and iso-paraffins) or Shellsol T (mixture of iso-paraffins) commercially available.

Particularly preferred mixtures according to the invention which comprise one or more hydrocarbons preferably comprise (a) a total amount of the hydrocarbon or hydrocarbons (eg in the form of a mineral oil, in particular a diesel fuel) of at least 80% by weight, preferably at least 90% by weight. , preferably at least 95% by weight, more preferably at least 98% by weight, and preferably, (b) a total amount of marking agent or formula (I) in the range from 10 ppm to 1000 ppm, preferably in the range of 25 ppm to 250 ppm, and more preferably in the range 30 ppm to 100 ppm, each based on the total weight of the mixture.

The invention also relates to the use of one or more compounds of the formula (I)

(I) where R ¹ , R ² and Y have the abovementioned meaning, preferably one of the meanings given above as preferred, as a marking agent for hydrocarbons, in particular for petroleum-derived fuels or lubricants. With regard to the preferred hydrocarbons or the preferred (preferably obtained from petroleum) hydrocarbon mixtures, reference is made to the above statements, which apply here accordingly.

The invention further relates to a method for labeling a hydrocarbon or a hydrocarbon mixture (and optionally identifying the labeled hydrocarbon or the marked mixture), in particular for marking a petroleum-derived fuel or lubricant, comprising the following step:

Adding an amount of one or more compounds of the formula (I)

(I)

wherein R ¹ , R ² and Y are as defined above, to the hydrocarbon or the hydrocarbon mixture, wherein the total added amount of the compound or compounds of formula (I) is sufficient to the compound or compounds of formula (I) in the mixture by Schiff's reagent.

Preferably, in a process according to the invention the proviso applies: A mixture according to the invention in the form of a fuel comprising 1-ethoxyethyl acetate or 1-methoxyethyl acetate does not comprise a lead-containing anti-knock agent. Alternatively or additionally preferred is a process according to the invention, for which the following applies: The mixture does not consist of 5-35% by weight of acetaldehyde diethyl acetal, 2-8% by weight of dibutyl ether, 10-35% by weight of alcohol and 22-83% by weight. -% kerosene or light oil.

Particularly preferred is a method according to the invention, for which both provisos mentioned above apply simultaneously.

Very particular preference is given to a process which comprises: A mixture according to the invention in the form of a fuel comprising a compound of the formula (I) in which Y is C = O does not comprise a lead-containing anti-knock agent. At the same time, preferably, a mixture according to the invention comprising kerosene or light oil is preferably free of acetaldehyde diethyl acetal.

Particularly preferred is a method according to the invention, for which the following applies: The mixture does not comprise a lead-containing anti-knock agent. At the same time, the following applies preferably: A mixture comprising kerosene or light oil is free from acetaldehyde diethyl acetal.

With regard to the preferred hydrocarbons or the preferred (preferably derived from petroleum) hydrocarbon mixtures, reference is again made to the above statements, which apply here accordingly.

In a method according to the invention for labeling a hydrocarbon or a hydrocarbon compound, the amount of the one or more compounds of the formula (I) is preferably in the form of a mixture according to the invention which, in addition to the marking agent, also comprises one of the preferred solvents or diluents Hydrocarbon or the hydrocarbon mixture.

A hydrocarbon marked according to the invention or a hydrocarbon mixture marked according to the invention is preferably identified by reaction with Schiff's reagent. A preferred method according to the invention for labeling a hydrocarbon or a hydrocarbon mixture and identifying the labeled hydrocarbon or the marked hydrocarbon mixture comprises the following identification steps:

Adding from 0.01 to 1.0 parts by weight, preferably 0.05 to 0.5 parts by weight and more preferably 0.1 to 0.25 parts by weight of fusch- sinschwefeliger acid (Schiff's reagent) (in particular in commercial form) to 1, 0 Parts by weight of a mixture according to the invention which has been marked by the process according to the invention and comprises one or more marking agents of the formula (I) in addition to the hydrocarbon or hydrocarbons,

Shaking the detection mixture thus obtained, preferably for a period in the range of 15 seconds to 3 minutes, preferably for a period in the range of 30 seconds to 2 minutes,

after completion of the agitation, allow a phase separation in the reaction mixture and check the aqueous (lower) phase for a color change (usually associated with a color well).

In a preferred method of the invention for identifying a labeled hydrocarbon or a labeled hydrocarbon mixture, the level of label in the mixture is quantified. A corresponding method comprises the following additional step (after reaction with Schiff's reagent):

photometric measurement of the aqueous phase against a solution of known concentration.

The compounds of the formula (I) to be used according to the invention can be prepared in a simple manner and thus provide inexpensive and readily available In contrast to the resulting from hydrolysis aldehydes they behave in mixtures with hydrocarbons to be marked (especially in the above-mentioned hydrocarbon mixtures such as mineral oils such as diesel or the like) extremely compatible, stable and unobtrusive.

Further aspects of the present invention will become apparent from the appended claims.

The following examples are intended to explain the invention in more detail. Unless otherwise indicated, all data are by weight.

Example 1: Detection reaction of 1-ethoxyethyl acetate in diesel fuel

1-Ethoxyethylacetat of the formula (Ia) was detected in diesel fuel according to DIN EN 590 with fuchsinschwefeliger acid (Schiff reagent).

It was used diesel fuel, namely commercial, ready-to-use diesel fuel, which contained a total of about 500 ppm of conventional additives: flow improvers (flow improvers, anti-settling, here: WASA), oxidation inhibitors, metal deactivators, corrosion inhibitors, foam inhibitors (anti-foam ), Ignition accelerators, detergents, biocides.

Each 10.0 g of this diesel fuel were with

(a) 0 ppm (without additive, reference sample),

(b) 100 ppm,

(c) 50 ppm,

(d) 30 ppm 1-Ethoxyethylacetat the formula (Ia) is added to produce a mixture according to the invention, which in addition to a hydrocarbon mixture also contains a compound of formula (I) (here: compound of formula (Ia)).

To the mixture according to the invention 2.0 g fuchsinschwefelige acid (Schiff's reagent) was added and shaken for 1 minute. Thereafter, the phases separated and the color change of the lower aqueous phase was evaluated. The results are shown in the following table:

As can be seen from the table, a dosage of 30 ppm of 1 - ethoxyethyl acetate in diesel fuel, after carrying out the detection reaction, already showed a clear color change with a corresponding color deepening.

The aqueous phase was photometrically measured against a solution of known concentration of product dye and quantified here by the amount of 1-ethoxyethyl acetate.

Example 2 Stability Study of 1-Ethoxyethyl Acetate (Formula (Ia) in Diesel Fuel According to DIN EN 590)

Diesel fuel (see Example 1) was admixed with 0.1% by weight or 1.0% by weight of 1-ethoxyethyl acetate of the formula (Ia) and then added

(a) 6 ° C / dark (b) room temperature (RT, approx. 20 ° C) / window (ie standing at the window, depending on the weather, temporarily exposed to direct sunlight), and

(c) 40 ° C / dark

stored. Subsequently, the content of 1-ethoxyethyl acetate of the formula (Ia) was determined in each case against an internal standard by gas chromatography in each case after 1, 2 and 4 weeks. The results are shown in the following table.

As can be seen from the table, 1-ethoxyethyl acetate in the doses 0.1% by weight and 1.0% by weight in diesel fuel over a period of 4 weeks shows very good stability.

Claims

claims: 1. Mixture comprising one or more hydrocarbons, a marking agent for the hydrocarbon (s) as well as preferably one or more further additives, wherein the labeling agent comprises one or more compounds of the formula (I) or consists of one or more compounds of the formula (I)

(I) in which R ^{1 is} a branched or unbranched alkyl group having 1 to 6 C atoms, preferably a branched or unbranched alkyl group having 1 to 5 C atoms, particularly preferably an unbranched alkyl group having 1 to 3 C atoms and especially preferably ethyl, R ^{2 is} H or a branched or unbranched alkyl group having 1 to 6 C atoms, preferably H or a branched or unbranched alkyl group having 1 to 5 C atoms, more preferably an unbranched alkyl group having 1 to 3 C atoms, and particularly preferred Methyl, and Y is CH ₂ , CH-CH ₃ or C = O, preferably CH ₂ or C = O, more preferably C = O. 2. Mixture according to claim 1, with the provisos: a fuel-formed mixture comprising 1-ethoxyethyl acetate or 1-methoxyethyl acetate does not contain a lead-containing anti-knock agent; the mixture does not consist of 5 to 35% by weight of acetaldehyde diethyl acetal, 2 to 8% by weight of dibutyl ether, 10 to 35% by weight of alcohol and 22 to 83% by weight of kerosene or light oil. 3. Mixture according to one of the preceding claims, wherein the marking agent comprises one or more compounds of formula (I) or consists of one or more compounds of formula (I), wherein R ^{1 is} a branched or unbranched alkyl group having 1 to 5 C atoms, R ^{2 is} H or a branched or unbranched alkyl group having 1 to 5 C atoms and Y is CH ₂ or C = O. 4. Mixture according to one of the preceding claims, wherein the marking agent comprises one or more compounds of formula (I) or consists of one or more compounds of formula (I), wherein R ^{1 is} an unbranched alkyl group having 1 to 3 C atoms, R ^{2 is} an unbranched alkyl group having 1 to 3 C atoms and YC = O means. 5. Mixture according to one of the preceding claims, wherein the marking agent comprises one or more compounds of formula (I) or consists of one or more compounds of formula (I), wherein in the compound of formula (I) or in one of the compounds of the formula (I) R ^{1 is} ethyl, R ^{2 is} methyl and Y C = O means. 6. Mixture according to one of the preceding claims, further comprising a substance from one of the following groups L1 and L2 or a mixture of substances from both groups L1 and L2, consisting of: (L1) isopropyl myristate, benzyl benzoate, diethyl phthalate and mixtures thereof, (L2) isododecane, n-paraffins having 9 to 14 carbon atoms, iso-paraffins having 9 to 14 carbon atoms, naphthalene, alkylnaphthalenes (especially methylnaphthalenes) and mixtures thereof. 7. Mixture according to one of the preceding claims, comprising a petroleum-derived fuel or lubricant containing a plurality of hydrocarbons. A blend according to any one of the preceding claims comprising a petroleum derived fuel or lubricant selected from the group consisting of gasoline, kerosene, diesel, fuel oil and engine oil. A blend according to any one of the preceding claims, comprising, in a total concentration in the range of from 0.0001 to 2% by volume, based on the total volume of the blend, of one or more additives selected from the group consisting of: flow improvers, oxidation inhibitors (antioxidants) . Metal deactivators, corrosion inhibitors, antifoaming agents, ignition accelerators, detergents, particulate reducing agents, anti-knock agents, anti-carburetor additives, anti-repellence agents, smoke reducing agents, biocides, conductivity improvers, burn-off aids, fragrances, anti-wear agents and viscosity improvers. 10. Mixture according to one of the preceding claims, comprising (a) a total amount of the hydrocarbon or hydrocarbons of at least 80% by weight, preferably at least 90% by weight, preferably at least 95% by weight, particularly preferably at least 98% by weight, and preferably (b) a total amount of labeling agent (s) in the formula (I) in the range of 10 ppm to 1000 ppm, preferably in the range of 25 ppm to 250 ppm, and more preferably in the range of 30 ppm to 100 ppm, in each case based on the total weight of the mixture. 1 1. Mixture comprising based on the total weight of the mixture 40 to 95 wt .-%, preferably 50 to 90 wt .-% of one or more compounds of formula (I)

(I) wherein R ¹ , R ² and Y have the meaning given in claims 1 and 3 to 5, such as a substance from one of the following groups L1 and L2 or a mixture of substances from both groups L1 and L2, consisting of: (L1) isopropyl myristate, benzyl benzoate, diethyl phthalate and mixtures thereof, (L2) isododecane, n-paraffins having 9 to 14 carbon atoms, iso-paraffins having 9 to 14 carbon atoms, naphthalene, alkylnaphthalenes (especially methylnaphthalenes) and mixtures thereof. 12. Use of one or more compounds of the formula (I)

(I) wherein R ¹ , R ² and Y have the meaning given in claims 1 and 3 to 5, as a marking agent for hydrocarbons, in particular for petroleum-derived fuels or lubricants. 13. A method for marking a hydrocarbon or a hydrocarbon mixture, in particular for petroleum-derived fuels or lubricants, comprising the following step: Adding an amount of one or more compounds of the formula (I)

(I) wherein R ¹ , R ² and Y have the meaning given in claims 1 and 3 to 5, to the hydrocarbon or the hydrocarbon mixture, wherein the total amount of the compound or compounds added sufficient to the compound or the compounds of formula ( I) in the mixture by Schiff's reagent to prove. 14. The method of claim 13, with the provisos: a fuel-formed mixture comprising 1-ethoxyethyl acetate or 1-methoxyethyl acetate does not comprise a lead-containing anti-knock agent; the mixture does not consist of 5 to 35% by weight of acetaldehyde diethyl acetal, 2 to 8% by weight of dibutyl ether, 10 to 35% by weight of alcohol and 22 to 83% by weight of kerosene or light oil. 15. The method of claim 13 or 14, wherein the amount of the one or more compounds of formula (I) is added in the form of a mixture according to claim 10 to the hydrocarbon or the hydrocarbon mixture. The process of any of claims 13 to 15, further comprising the following step of identifying the labeled hydrocarbon or hydrocarbon mixture: Reacting the labeled hydrocarbon or hydrocarbon mixture with Schiff's reagent.