DE4424712A1 - Use of benzaldehydes to mark hydrocarbons - Google Patents

Abstract

The invention relates to the use of benzaldehydes of the formula (I), in which ring A can be benzo-anellated and R<1>, R<2> and R<3> are hydrogen, hydroxy, C1-C15 alkyl, C1-C15 alkoxy, cyano, nitro or a radical of the formula NR<4>R<5> or COOR<6>, in which R<4> is hydrogen or possibly substituted C1-C15 alkyl, R<5> is possibly substituted C1-C15 alkyl or a radical of the formula L-NX<1>X<2>, in which L is C2-C8 alkylene and X<1> and X<2> are mutually independently C1-C6 alkyl or, together with the nitrogen atom bonding them, a heterocyclic radical, and R<6> is hydrogen, possibly substituted C1-C15 alkyl or a radical of the formula L-NX<1>X<2>, in which L, X<1> and X<2> have the above meanings, as marking agents for hydrocarbons, a process for detecting these benzaldehydes in hydrocarbons and hydrocarbons containing the above benzaldehydes.

Description

The present invention relates to the use of benz aldehydes of the formula I.

in the
ring A can be fused to benzo
R¹, R² and R³ each independently represent hydrogen, hydroxy, C₁-C₁₅ alkyl, C₁-C₁₅ alkoxy, cyano, nitro or a radical of the formula NR⁴R⁵ or COOR⁶, in which
R⁴ represents hydrogen or C₁-C₁₅ alkyl, which can be interrupted by 1 to 4 oxygen atoms in ether function and is optionally substituted by phenyl,
R⁵ for C₁-C₁₅-alkyl, which can be interrupted by 1 to 4 oxygen atoms in ether function and optionally substituted by phenyl, or a radical of the formula L-NX¹X², where L is independently the meaning of C₂-C₈-alkylene and X¹ and X² each have the meaning of C₁-C₆-alkyl or together with the nitrogen atom connecting them the meaning of a 5- or 6-membered ge saturated heterocyclic radical, which may still contain an oxygen atom in the ring, and
R⁶ represents hydrogen, C₁-C₁₅ alkyl, which can be interrupted by 1 to 4 oxygen atoms in ether function, or a radical of the formula L-NX¹X², in which L, X¹ and X² each have the abovementioned meaning,
as a marking agent for hydrocarbons, a method for the detection of these benzaldehydes in hydrocarbons and hydrocarbons, containing the above-mentioned benzaldehydes.

From US-A-5 145 573, US-A-5 182 372 and EP-A-499 845 Azo dyes are already known as markers for Mineral oils. In US-A-4 009 008 a Ver drive to mark mineral oils using disazo dyes described in which one added the dye to the mineral oil visualized by placing an adsorbent on the marked Mineral oil adds, the other colored components of the mineral oil binds.

In DE-A-36 08 215 and DE-A-37 24 757 are Benzopyranderi vate and their use in recording systems.

In example 1 of DE-A-36 08 215 is the implementation of 2,3-di methylbenzopyrylium trichlorozincate with 4-dimethylaminobenzal dehyd in methanol to form the color salt of the formula

described.

WO-A-11 466/1994 describes the use of substituted Anilines described for marking mineral oils.

The object of the present invention was to develop new means of mar to provide hydrocarbons. The new means should be easily accessible and readily soluble in hydrocarbons his. They should also be demonstrated in a simple manner can. Even very small amounts of marking should be used be made visible through a strong color reaction can.

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

All alkyl and in the formula I mentioned above Alkylene radicals can be both straight-chain and branched.  

When X¹ and X² together with the nitrogen atom connecting them a 5- or 6-membered saturated heterocyclic radical which can still contain an oxygen atom in the ring, so can NEN z. B. pyrrolidinyl, piperidinyl or morpholinyl in Be come.

R¹, R², R³, R⁴, R⁵, R⁶, X¹ and X² are z. B. methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopen tyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.

R¹, R², R³, R⁴, R⁵ and R⁶ are still z. B. heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, Undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotrides cyl, tetradecyl or pentadecyl (the above designations Iso octyl, isononyl, isodecyl and isotridecyl are trivial names genes and come from the alcohols obtained after oxosynthesis - see. also Ullmann’s Encyclopedia of Industrial Chemistry, 5th Edition, Vol. Al, pages 290 to 293, and Vol. A 10, pages 284 and 285).

Residues R¹, R² and R³ are still z. B. methoxy, ethoxy, propoxy, Isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyl oxy, neopentyloxy, tert-pentyloxy, hexyloxy, 2-methylpentyloxy, Heptyloxy, octyloxy, 2-ethylhexyloxy, isooctyloxy, nonyloxy, iso nonyloxy, decyloxy, isodecyloxy, undecyloxy, dodecyloxy, tride cyloxy, 3,5,5,7-tetramethylnonyloxy, isotridecyloxy, tetradecyl oxy or pentadecyloxy.

R⁴ and R⁵ are still z. B. 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-meth oxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxy butyl, 2- or 4-propoxybutyl, 2- or 4-butoxybutyl, 3,6-dioxa heptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 3,6,8-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatri decyl, benzyl or 1- or 2-phenylethyl.

L are z. B. (CH₂) ₂, (CH₂) ₃, (CH₂) ₄, (CH₂) ₅, (CH₂) ₆, (CH₂) ₇, (CH₂) ₈, CH (CH₃) CH₂ or CH (CH₃) CH (CH₃).

Benzaldehydes of the formula I are preferred according to the invention used, in which at least one of the radicals R¹ to R³ one The remainder of the formula NR⁴R⁵ means, wherein R⁴ and R⁵ each have the above have the meaning given.  

Benzaldehydes of the formula Ia are particularly preferred

in which R¹, R², R⁴ and R⁵ each have the abovementioned meaning zen, used for marking hydrocarbons.

Benzaldehydes of the formula Ia in which R 1 and R² independently of one another are each hydrogen, hydroxy, C₁-C₁₅ alkyl, C₁-C₁₅ alkoxy or a radical of the formula COOR⁶, wherein R⁶ has the meaning given above, R⁴ is hydrogen or C₁-C₁₅ alkyl and R⁵ are C₁-C₁₅ alkyl.

Benzaldehydes of the formula Ia in which R in are particularly preferred and R⁵ are each independently C₁-C₁₃ alkyl, and R¹ and R² each represent hydrogen, for marking hydrocarbons fen used.

The invention also relates to a method for detection the presence of benzaldehydes of formula I in hydrocarbon substances, the hydrocarbon with an aqueous alcohol tical or alcoholic medium that contains a proton acid, at least one compound from the group of compounds gene consisting of substituted benzopyrylium salts of For mel II

in the R⁷ for C₁-C₈ alkyl, phenyl, C₁-C₅ alkoxy or halogen and R und represent methyl or R⁷ and R⁸ together for 1,4-butylene and the Ring B can be fused by a benzene ring and given if by C₁-C₄-alkyl, pyrrolidino, piperidino, morpholino, Chlorine or bromine or in ring position 7 if necessary also Hydroxy, C₁-C₄ alkoxy, C₁-C₅ mono- or dialkylamino, each can in turn be substituted by chlorine or phenyl, substi is tuiert and X⊖ means any anion, and indoles the Formula III  

in which R⁹ and R¹⁰ each independently represent hydrogen, hydroxy, a radical of the formula NR⁴R⁵, in which R⁴ and R⁵ each have the abovementioned meaning, are C₁-C--alkyl, phenyl, C₁-C₅-alkoxy or halogen,
and optionally containing a halide of the metals zinc, aluminum or tin.

According to the invention, preference is given to indoles of the formula III, ins special 2-phenylindole used.

Examples of suitable anions X⊖ are tetrachlorozincate, halo genide, sulfate, tetrafluoroborate or phosphate.

The Benzaldehyde I, the Benzopyryliumsalze II and the In dole III are usually known per se.

Under marking in the sense of the invention is an addition of Benzaldehydes of formula I in such a concentration to coal water to understand that the hydrocarbons thereby for the human eye either not at all or only a little are visibly stained, but the benzaldehydes of For mel I easily by the detection methods described here and are clearly visible.

Another object of the present invention are coals Hydrogen containing one or more of the benzaldehydes Formula I.

Among hydrocarbons in the sense of the invention are alipha to understand table or aromatic hydrocarbons that be in a liquid state under normal conditions.

These are in particular mineral oils, for example fuels, such as gasoline, kerosene or diesel oil, or oils such as heating oil or Mo. gate oil.

The benzaldehydes of formula I are particularly suitable for mar mineral oils for which labeling 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, the benzaldehydes Formula I either in substance or in the form of solutions turns. Organic solvents are suitable as solvents. Aromatic hydrocarbons, such as toluene, Xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of herer aromatics, which is sold under the name Shellsol® AB (Shell) is customary to use. To ensure a high viscosity of the resul avoiding solutions, one generally chooses one Concentration of benzaldehydes I from 5 to 80% by weight, based on the solution.

To improve the solubility, other Cosol valves, e.g. B. alcohols, such as methanol, ethanol, propanol, iso propanol, 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-di methylaniline, toluidine or xylidine, alkanolamines, such as 3- (2-meth oxyethoxy) propylamine, o-cresol, m-cresol or p-cresol, ketones, such as diethyl ketone or cyclohexanone, lactams such as γ-butyrolactone, Carbonates, such as ethylene carbonate or propylene carbonate, phenols, such as t-butylphenol or nonylphenol, esters such as methyl phthalate esters, ethyl phthalate, (2-ethylhexyl) phthalate, Ethyl acetate, butyl acetate or cycloacetic acid hexyl esters, amides such as N, N-dimethylformamide, N, N-diethylacetamide or N-methylpyrrolidinone, or mixtures thereof who used the.

By means of the benzaldehydes of For mel I is very easy to replenish labeled hydrocarbons assign, even if the labeling substances only in one con concentration of about 10 ppm or less.

Evidence of the presence of applied as marking substances Compounds of formula I succeed in hydrocarbons partial if you mix the hydrocarbon with an aqueous alcohol tical or alcoholic medium treated with a pyrylium salt of formula II and / or an indole of formula III, a protonic acid and optionally a halide of the metals zinc, aluminum or Contains tin. When using aqueous-alcoholic media the weight ratio water: alcohol is 0.5: 1 to 4: 1, preferably approx. 1: 1. A clear view results bare color change of the aqueous-alcoholic phase.  

Suitable alcohols are e.g. B. ethanol, propanol, isopropanol, 1-methoxypropan-2-ol, ethylene glycol or 1,2- or 1,3-propylene glycol. The use of ethanol is preferred.

Suitable protonic acids for the processes according to the invention are in particular so-called strong acids, d. H. Protonic acids thereof pKa is 3.5. Examples of such acids are anor ganic or organic acids, such as perchloric acid, iodine water Substance acid, hydrochloric acid, hydrobromic acid, river acid, sulfuric acid, nitric acid, phosphoric acid, benzenesulfone acid, toluenesulfonic acid, naphthalenesulfonic acid, methanesulfone acid, oxalic acid, maleic acid, chloroacetic acid, dichloroacetic acid or bromoacetic acid. In some cases it can be from Be an advantage of these acids, e.g. B. by adding acetic acid buffer.

In addition to o- or p-toluenesulfonic acid, particularly inorganic ones To emphasize acids, with hydrochloric acid or sulfuric acid in particular their meaning is important.

Suitable halides of the metals zinc, aluminum or tin are e.g. B. zinc chloride, zinc bromide, aluminum chloride, aluminum bromide or tin tetrachloride. Zinc chloride is particularly noteworthy.

It is usually sufficient to use an amount of approximately 10 to 50 ml of the Hydrocarbon labeled according to the invention with 1 to 50 ml an aqueous-alcoholic or alcoholic solution of a pyry lium salt of the formula II and / or an indole of the formula III, a protonic acid, optionally with the addition of the metal halogen nids, shake to get a color change. It is also possible, instead of the solution of the protonic acid, an aqueous al to use alcoholic solution of the metal halide alone because this also reacts sourly.

The concentration of the protonic acid in the aqueous-alcoholic or alcoholic solution is usually 5 to 50% by weight, preferably 10 to 30% by weight. The concentration on Metal halide is generally 0 to 50% by weight preferably at 5 to 20 wt .-%, each based on the weight the solution.

A great advantage of the invention is that two ver different methods for the detection of benzaldehydes of the formula I be can be used. Evidence can therefore also be provided for possible Very reliable interference (e.g. additives in diesel fuel) be carried out.

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

General regulation 1

Commercial diesel fuel was one with 10 ppm each Benzaldehyde added. For this purpose, the aldehyde was 0.1% by weight in Pre-dissolved toluene and added this solution to the diesel fuel.

In the following Examples 1 to 12, 10 ml each were so mar kiert diesel fuel with 2 ml of reagent solution and Shaken for 5 minutes. Then 1 ml of water was added and shaken for another 5 minutes. The aqueous phase showed the colors indicated in the following table No. 1.

Reagent solution 1:

5 ml of 1% by weight indole in ethanol
5 ml hydrochloric acid conc.
5 g zinc chloride
95 ml acetic acid

Reagent solution 2:

5 ml of 1% by weight 2-methylindole in ethanol
5 ml hydrochloric acid conc.
5 g zinc chloride
95 ml acetic acid

Reagent solution 3:

5 ml of 1% by weight 2-phenylindole in ethanol
5 ml hydrochloric acid conc.
5 g zinc chloride
95 ml acetic acid

Particularly advantageous results are obtained if the die fuel is first filtered through silica gel.  

Table No. 1

Similar favorable results can be achieved if you look at the following Table No. 2 listed benzaldehydes as Markie applies.

Table No. 2

General regulation 2

Commercial diesel fuel was with 10 ppm benzal dehydrated. For this purpose, the benzaldehyde was 0.1% by weight in Pre-dissolved toluene and added this solution to the diesel fuel.

In Examples 21 to 30 10 ml each of the labeled Diesel fuel mixed with 2 ml of reagent solution 4 and 5 minutes heated under reflux. Then 1 ml of water / Etha nol (1: 1 v / v) added and shaken for a further 5 minutes. The aqueous phase showed that indicated in the following Table No. 3 level color.

Reagent solution 4:

5 ml of benzopyrylium salt of the formula

1% by weight in water
25 ml hydrochloric acid conc.
225 ml acetic acid

Table 3

Similar favorable results are achieved if you do this in Reagent solution 5 contained benzopyrylium salt by that of the formula

replaced.

Claims (5)

1. Use of benzyldehydes of the formula I in the
the ring A can be fused to benzo and
R¹, R² and R³ each independently represent hydrogen, hydroxy, C₁-C₁₅ alkyl, C₁-C₁₅ alkoxy, cyano, nitro or a radical of the formula NR⁴R⁵ or COOR⁶, in which
R⁴ represents hydrogen or C₁-C₁₅ alkyl, which can be interrupted by 1 to 4 oxygen atoms in ether function and is optionally substituted by phenyl,
R⁵ for C₁-C₁₅-alkyl, which can be interrupted by 1 to 4 oxygen atoms in ether function and optionally substituted by phenyl, or -a radical of the formula L-NX¹X², where L is C₂-C₈-alkylene and X¹ and X² independently of one another each have the meaning of C₁-C₆-alkyl or, together with the nitrogen atom connecting them, have the meaning of a 5- or 6-membered saturated heterocyclic radical which may still contain an oxygen atom in the ring, and
R⁶ represents hydrogen, C₁-C₁₅-alkyl, which can be interrupted by 1 to 4 oxygen atoms in ether function, or a radical of the formula L-NX¹X², in which L, X¹ and X² each have the abovementioned meaning,
as a marking agent for hydrocarbons. 2. Use of benzaldehydes according to claim 1, characterized in that the benzaldehydes of the formula Ia correspond in which R¹, R², R⁴ and R⁵ each have the meaning given in claim 1. 3. Use of benzaldehydes according to claims 1 or 2, characterized in that R¹ and R² are independent of each other are each hydrogen, hydroxy, C₁-C₁₅ alkyl, C₁-C₁₅ alkoxy or a radical of the formula COOR⁶, wherein R⁶ ge in claim 1 ge has mentioned meaning, R⁴ is hydrogen or C₁-C₁₅ alkyl and R⁵ is C₁-C₁₅ alkyl. 4. A method for detecting the presence of benzaldehydes of the formula I according to claim 1 in hydrocarbons, characterized in that the hydrocarbon is treated with an aqueous alcoholic or alcoholic medium which is a protonic acid, at least one compound from the group of compounds consisting of substituted pyrylium salts of formula II in the R⁷ for C₁-C₈ alkyl, phenyl, C₁-C₅ alkoxy or halogen and R⁸ for methyl or R⁷ and R⁸ stand together for 1,4-butylene and the ring B can be fused by a benzene ring and optionally by C₁ -C₄-alkyl, pyrrolidino, piperidino, morpholino, chlorine or bromine or in ring position 7 if appropriate also by hydroxy, C₁-C₄-alkoxy, C₁-C₅-mono- or dialkylamino, which in turn can each be substituted by chlorine or phenyl, is substituted and X⊖ denotes an anion, and indoles of the formula III in which R⁹ and R¹⁰ each independently represent hydrogen, a radical of the formula NR⁴R⁵, where R⁴ and R⁵ each have the meaning given in Claim 1, are C₁-C₈-alkyl, phenyl, C₁-C₅-alkoxy or halogen,
and optionally containing a halide of the metals zinc, aluminum or tin. 5. hydrocarbons containing a as a marking agent or more benzaldehydes of the formula I according to claim 1.