SK5197A3 - Use of benzaldehyde derivative to mark hydrocarbons, proofing method for the benzaldehyde derivative presence in hydrocarbons and hydrocarbons containing the benzaldehyde derivative - 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 use of a benzaldehyde derivative for the labeling of hydrocarbons, a method for demonstrating the presence of a benzaldehyde derivative in hydrocarbons and hydrocarbons containing a benzaldehyde derivative.

Technical field

The invention relates to the use of benzaldehyde derivatives for the labeling of hydrocarbons, to a method for the detection of these benzaldehyde derivatives in the hydrocarbons and hydrocarbons which are labeled with such benzaldehyde derivatives.

BACKGROUND OF THE INVENTION

U.S. Pat. Nos. 5,145,573 and 5,182,372; No. 499,845 are already known azo dyes which are used as marking mineral oils. U.S. Pat. No. 4,009008 discloses a process for labeling mineral oils with diazo dyes, wherein the colorant added to the mineral oils is visualized by adding an adsorbing agent to the labeled mineral oil that binds other color portions of the mineral oil.

In German Pat. DE-A-3 608 215 and DE-A-3 724757 disclose benzopyran derivatives and their use in labeling systems.

In Example 1 of German patent no. DE-A-3 608215 describes the reaction of 2,3-dimethylbenzopyrylium trichloro-zincate with

4-dimethylaminobenzaldehyde in methanol to form a colored salt of formula

©

In World Pat. WO-A-11 466/1994 describes the use of substituted anilines for marking mineral oils.

It is an object of the present invention to provide a novel means for marking hydrocarbons. The new composition should be readily available and readily soluble in hydrocarbons. In addition, it should be easily detectable. Such a composition should also be visualized in a minimal amount by a strong staining reaction.

Surprisingly, it has been found that the benzaldehydes of the invention are very preferred hydrocarbon labeling agents.

SUMMARY OF THE INVENTION

The invention relates to the use of the benzaldehyde derivatives of the general formula I

where

A represents a benzoellated ring,

R ¹ , R ² and R ³ are each independently hydrogen, hydroxyl, C 1 -C 15 alkyl, C 1 -C 15 alkoxy, cyano, nitro, NR ⁴ R ⁵ or COOR ⁶ , where

R ⁴ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms optionally interrupted by up to 4 oxygen atoms in the ether bond and optionally substituted by a phenyl group represents an alkyl group having 1 to 15 carbon atoms optionally interrupted by 1 and is optionally substituted with a phenyl group, or a group of formula LNX ³ X ² , wherein L is an alkylene group having 2 to 8 carbon atoms and X and X are each independently an alkyl group having 1 to 6 carbon atoms carbon atoms, or together with the nitrogen atom to which they are attached, form a 5- or 6-membered saturated heterocyclic group which optionally contains an oxygen atom in the ring,

R ⁶ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms optionally interrupted by 1 to 4 oxygen atoms in the ether bond, or a group of the formula LNX-Lx ² wherein L, X ¹ and X ² are as defined above , for the labeling of hydrocarbons.

The invention also relates to a method for detecting these benzaldehyde derivatives in hydrocarbons and hydrocarbons which are labeled with such derivatives.

All alkyl or alkylene groups or moieties which occur in the above general formula (I) have a straight or branched chain.

When X ¹ and X ² together with the nitrogen atom to which they are attached represent a 5- or 6-membered saturated heterocyclic group which optionally contains an oxygen atom in the ring, the group may be pyrrolidinyl, piperidinyl or morpholinyl.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , x ¹ and X ^{2 include} , by way of example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, a neo-pentyl, tert-pentyl, hexyl or 2-methylpentyl group.

Further, R ¹ , R ² , R ³ , R ⁴ , R ^5, and Ŕ ⁶ are, for example, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, undecyl, dodecyl, tridecyl, The 5,5,7-tetramethylnonyl, isotridecyl, tetradecyl or pentadecyl group (the aforementioned labels isooctyl, isononyl, isodecyl and isotridecyl groups are trivial labels and are derived from alcohols prepared by oxosynthesis as described in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition. A1, pp. 290-293 and volume A10 pp. 284-285).

R ² and R ³

Further examples of R ^J include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy, thyloxy,

2-methylpentyloxy, Hep2-ethylhexyloxy, izookizononyloxyskupina, decyloxyhexyloxyskupina, octyloxy, nonyloxy group izodecyloxyskupina, undecyloxyskupina, dodecyloxy, tridecyloxyskupina, 3,5,5,7-tetrametylnonyloxyskupina, izotridecyloxyskupina, tetradecyloxy and pentadecyloxyskupina.

R ⁴ and R ⁵ can furthermore be, for example, 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, 2- or 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7- dioxaoktylovú.

3.7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl,

4,8-dioxadecyl, 3,6,8-trioxadecyl, 3,6,9-trioxaundecyloxy, 3,6,9,12-tetraoxatridecyl, benzyl or 1- or

2-phenylethyl.

L is, for example, a group of formula (CH ₂ ) ₂ , (CH ₂ ) ₃ , (CH ₂ ) ₄ , (ch ₂ ) ₅ , (ch ₂ ) ₆ , (ch ₂ ) ₇ , (ch ₂ ) ₈ , ch (ch ₃ ) (ch ₂ ) or ch (ch ₃ ) ch (ch ₃ ).

According to the invention, the preferred benzaldehydes of the formula I, wherein is at least one R ¹ to R ³ a group of the formula NR ⁴ R ⁵ wherein R ⁴ and R ⁵ are as defined above.

According to the invention, the benzaldehydes of the general formula Xa are particularly preferred for marking mineral oils

(Ia) wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above.

According to the invention, particularly preferred benzaldehydes of general formula Ia, wherein R ^A and R are, independently of one another are H, OH, an alkyl group containing l to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, or a group of the formula COOR ⁶ wherein R ⁶ is as defined above and wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms and R ⁵ represents an alkyl group having 1 to 15 carbon atoms.

According to the invention, the benzaldehydes of the general formula (Ia) in which R ⁴ and R ⁵ represent, independently of one another, an alkyl group containing 1 to 13 carbon atoms and R ¹ and R ² hydrogen atom are particularly preferred for the labeling of mineral oils.

According to the invention, a method for demonstrating the presence of benzaldehydes of the general formula I in hydrocarbons consists in treating the hydrocarbon with an aqueous-alcoholic or alcoholic medium containing a protonic acid, at least one compound of the substituted benzopyrylium salts of the general formula II

©, © (II) where

R ⁷ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or a halogen atom,

R ⁸ represents a methyl group;

R and R together represent a 1,4-butylene group and the ring B can be fused with a benzene ring and is optionally substituted with a C1-C4 alkyl group, a pyrrolidino group, a piperidino group, a morpholino group, a chlorine or bromine atom or hydroxyl, C 1 -C 4 alkoxy, monoalkylamino or C 1 -C 5 dialkylamino in the alkyl moiety optionally substituted by a chlorine atom or a phenyl group, and

X ^- represents any anion, indoles of formula III

III (III) where

R ⁹ and R ¹⁰ are each independently hydrogen, hydroxyl or NR ⁴ R ⁵ , wherein R ⁴ and R ⁵ are as defined above, (C 1 -C 8) alkyl, phenyl, alkoxy containing 1 to 5 carbon atoms or halogen, and optionally a zinc, aluminum or tin halide.

2-Phenylindole is particularly preferably used as the indole III.

Examples of suitable anions X 'include tetrachloro-zincate, halide, sulfate, tetrafluoroborate and phosphate.

The benzaldehydes of the formula I, the benzpyrylium salts of the formula II and the indoles of the formula III are generally known.

By designation according to the invention is meant the addition of the benzaldehyde derivatives of the formula I to hydrocarbons in an amount such that the hydrocarbons are either colored or only slightly visibly colored to the human eye, but the benzaldehyde derivatives of the formula I are clearly detectable in the manner described.

The invention also relates to hydrocarbons containing at least one benzaldehyde of the general formula I.

According to the invention, hydrocarbons are understood to be aliphatic or aromatic hydrocarbons which are normally in the liquid state. They are primarily mineral oils, for example propellants such as gasoline, kerosene or diesel or heating oils or motor oils.

The benzaldehydes of the formula I are particularly suitable for marking mineral oils for which labeling is required, for example for taxation reasons. In order to minimize the labeling costs, only a minimum amount of labeling agent is required.

The benzaldehyde derivatives of the general formula (I), either as such or in the form of solutions, are used for the labeling of hydrocarbons. Suitable solvents are organic solvents. Preferred are aromatic hydrocarbons such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatics under the trade name Shellsol ^R AB (Shell). In order to avoid the high viscosity of the solutions obtained, the weight concentration of the benzaldehyde derivatives of the general formula I is generally chosen from 5 to 80%, based on the solution as a whole.

Other solvents 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 methyl propylene glycol; amines such as triethylamine, diisooctylamine, dicyclohexylamine, aniline, N-methylaniline, Ν, Ν-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 τ-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, Ν, Ν-diethyl acetamide or N-methylpyrrolidone or mixtures thereof.

The use of the benzaldehyde derivatives of the formula I according to the invention makes it possible to very easily prove the labeled hydrocarbons even if the marker is only in a concentration of approximately 10 ppm or even lower.

The demonstration of the presence of the benzaldehydes of the formula I used in the hydrocarbons is preferably carried out by treating the hydrocarbon with an aqueous-alcoholic or alcoholic medium containing a pyrylium salt of formula II and / or an indole of formula III, protonic acid and optionally zinc, aluminum halide or tin. When using an aqueous-alcoholic medium, the weight ratio water: alcohol is 0.5: 1 to 4: 1, preferably about 1: 1. The water-alcohol phase is clearly visible.

Suitable alcohols include, by way of example, ethanol, propanol, isopropanol, 1-methoxypropan-2-ol, ethylene glycol, or the like.

1,2-propylene glycol or 1,3-propylene glycol. Ethanol is preferred.

Suitable protonic acids for the process according to the invention are particularly strong acids, i.e. protonic acids having a pKa < 3.5. Examples of such acids include inorganic and organic acids, such as perchloric, hydroiodic, hydrochloric, hydrobromic, hydrofluoric, sulfuric, nitric, phosphoric, benzenesulfonic, toluenesulfonic, naphthalenesulfonic, methanesulfonic, oxalic, maleic, dichloroacetic, chloroacetic, chloroacetic, chloroacetic, chloroacetic, chloroacetic. In many cases, it may be advantageous to buffer these acids by adding, for example, acetic acid.

In addition to o-toluenesulfonic and p-toluenesulfonic acids, inorganic acids such as hydrochloric acid and sulfuric acid are particularly preferred.

Suitable zinc, aluminum or tin halides include, for example, zinc chloride, zinc bromide, aluminum chloride, aluminum bromide or tin tetrachloride, with zinc chloride being particularly preferred.

As a rule, it is convenient to shake about 10 to 50 ml of the hydrocarbon of the invention with 1 to 50 ml of a water-alcoholic or alcoholic solution of the pyrylium salt of formula II and / or indole of formula III, protonic acid optionally with a metal halide. It is also possible to use an aqueous-alcohol solution of the metal halide itself instead of the protonic acid solution, since these metal halides also react acidically.

The weight concentration of the protonic acid in the aqueous-alcoholic solution or alcoholic solution is generally 5 to 50% and preferably 10 to 30%. The weight concentration of the metal halide is generally 0 to 50%, preferably 5 to 20%, based on the weight of the solution as a whole.

A great advantage of the invention is that two different methods can be used to determine the benzaldehyde of formula (I). The proof can therefore also be performed very reliably also in the case of possible disturbances (eg diesel fuel additives).

The following examples illustrate the invention in more detail, but do not limit it in any way.

DETAILED DESCRIPTION OF THE INVENTION

General Regulation 1:

Commercial diesel is mixed with 10 ppm benzaldehyde. To this end, 0.1 wt. of aldehyde in toluene and this solution is added to the diesel fuel.

In the following Examples 1 to 12, 10 ml of the diesel fuel thus designated are mixed with 2 ml of the reagent solution and shaken for 5 minutes. 1 ml of water is then added and the mixture is shaken for a further 5 minutes. The aqueous phase shows the color shown in the following Table I.

Reagent solution 1 ml 1 wt. solution of indole in ethanol 5 ml of concentrated hydrochloric acid 5 g of zinc chloride ml of acetic acid

Reagent solution 2 ml 1 wt. solution of 2-methylindole in ethanol 5 ml of concentrated hydrochloric acid 5 g of zinc chloride ml of acetic acid

Reagent solution 3 ml 1 wt. solution of 2-phenylindole in ethanol 5 ml concentrated hydrochloric acid 5 g zinc chloride ml acetic acid

Particularly good results are when the diesel is pre-filtered through diatomaceous earth. In the first column of the tables the example number is always given.

Table I

aldehyde Reagent Color 1 CKO Φ N (CH ₃ ) ₂ 1 'fuksínová 2 CHO Φ N (CH ₃ ) ₂ 2 purple 3 CKO Φ N (CH ₃ ) ₂ 3 purple 4 CKO N (C ₂ H _S ) ₂ 1 Orange 5 CHO φ '·· N (C ₂ H 5) ₂ 2 red violet

aldehyde Reagent Color 6 CHO 4 OHN (C ₂ H ₅ ) 2 3 fuksínová 7 CHO 0 1 oranxová 8 CHO φ <· about 2 červenofialová 9 CHO 0 3 fuksínová 10 CHO ₂ CH ₂ CH ₃ 9 N (CH ₃ ) ₂ 1 červenof ialová

aldehyde (Reagent Color 11 CKO Á. ^ CO ₂ CK ₃ 9 N (CH ₃ ) ₂ 2 modrof ialová 12 CHO 1 / CO ₂ CH ₃ 9 N (CH ₃ ) ₂ 3 blue-blue i

Similarly favorable results are obtained using the benzaldehydes as the labeling agents listed in Table II.

Table II

aldehyde 15 C HO with about 16 CHO Φ about 17 CHO Φ CH3-N-C2H4CN 18 CHO 1 OH Φ N (CH ₃ ) 2 19 CHO X OH Φ N ((CH ₂ C ₆ H ₅ ) ₂ 20 CHO 1 .och ₃ Φ N (C ₂ H ₅ ) ₂

General Regulation

Commercial diesel is mixed with 10 ppm benzaldehyde. To this end, 0.1 wt. of aldehyde in toluene and this solution is added to the diesel fuel.

In the following Examples 21 to 30, 10 ml of the diesel fuel thus designated are mixed with 2 ml of the reagent solution and heated under reflux for 5 minutes. 1 ml of water / ethanol (1: 1 by volume) is then added and the mixture is shaken for minutes. The aqueous phase exhibits the color shown in Table III below.

Reagent solution 4 ml 1 wt. of a solution of benzopyrylium salt in water of formula

ml of concentrated hydrochloric acid 225 ml of acetic acid

Table III

aldehyde Q Color 21 CHO Φ N (CH ₃ ) ₂ C ₆ H ₅ blue 22 CHO Φ N (CH ₃ ) ₂ ch ₃ blue

aldehyde Q Color 23 CHO 1 co ₂ ch ₃ in N (CH ₃ ) ₂ c ₆ h ₅ blue 24 1 as CHO ₂ CH ₃ N (CH _{3) 2} H blue 25 CHO cis N (C ₂ H ₅ ) ₂ CH ₃ blue 26 CHO Φ ' about ch ₃ blue _; 27 CHO 0 H blue

Aidehyd Q Color 28 CCA about OH ch ₃ červenof ialová 29 CHO Φ och ₃ ch ₃ red violet i 30 CHO Ψ “· och ₃ ch ₃ purple

Favorable results are also obtained with reagent solution 4 containing the benzopyrylium salt of formula

ZnCl ₃ ®

Θ

Industrial use

Use of benzaldehyde derivatives for the labeling of hydrocarbons, readily available and well soluble and readily detectable in hydrocarbons, even in small amounts, visible by a strong color reaction.

Claims (5)

PATENT CLAIMS Use of a benzaldehyde derivative of the general formula I wherein: A represents a benzoellated ring, R @ 1, R @ ² and R @ ² are each independently hydrogen, hydroxy, C1-C15 alkyl, C1-C15 alkoxy, cyano, nitro or NR; ⁴ R ⁵ or COOR ⁶ wherein R ⁴ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, which is optionally interrupted by 1 to 4 oxygen atoms in the ether bond and is optionally substituted by a phenyl group, R ⁵ represents an alkyl group having 1 to 15 carbon atoms which is optionally interrupted by 1 to 4 oxygen atoms in the ether bond and is optionally substituted by a phenyl group, or a group of formula LNX ^x X, wherein L represents an alkylene group containing 2 to 8 carbon atoms and X ¹ and X ² represent, independently of one another, an alkyl group containing 1 to 6 carbon atoms or, together with the nitrogen atom to which they are attached, form a 5- or 6-membered saturated heterocyclic group which may optionally contain a ring more O, it is H, an alkyl group having 1 to 15 carbon atoms, optionally interrupted by 1 to 4 oxygen atoms in ether bond, or R V2orca LNX -'- X ^2, wherein L, X and X 'are as defined above, for the designation of hydrocarbons. Use according to claim 1 of a benzaldehyde derivative of the general formula Ia (Ia) wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined above. Use according to claim 1 or 2 of a benzaldehyde derivative of the general formula Ia, wherein R ¹ and R ² represent independently of one another a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms or a group of the general formula C C Λ COOR wherein R 0 is as defined above and wherein R is hydrogen or C 1 -C 15 alkyl and R ⁵ is C 1 -C 15 alkyl. A method for detecting the presence of benzaldehydes of the general formula I in hydrocarbons, characterized in that the hydrocarbon is treated with an aqueous-alcoholic or alcoholic medium containing a protonic acid, at least one of the substituted benzopyrylium salts of the general formula II (II) R ⁷ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, R ⁸ represents a methyl group; R ⁷ and R ⁸ together are 1,4-butylene and piperidino, or the bromine or ring B can be fused with a benzene ring and is optionally substituted with C 1 -C 4 alkyl, pyrrolidino, morpholino, chloro in the 7-position of the ring optionally also hydroxyl, C 1 -C 4 alkoxy, C 1 -C 5 monoalkylamino or C 1 -C 5 dialkylamino, each optionally substituted by a chlorine atom or a phenyl group, and X is any anion, indoles of formula III RLO H R ⁹ (III) wherein R ⁹ and R ¹⁰ independently of one another represent a hydrogen atom, a hydroxyl group or a group of the formula NR ⁴ R ⁵ , where R ⁴ and R ⁵ are as defined above, an alkyl group having 1 to 8 carbon atoms, a phenyl group, an alkoxy group containing 1 to 5 carbon atoms or a halogen atom, and optionally a zinc, aluminum or tin halide. 5. Hydrocarbons comprising at least one benzaldehyde derivative of the formula I as claimed in claim 1.