HUT76687A - Use of benzaldehydes to mark hydrocarbons - Google Patents

Description

The present invention relates to the use of benzaldehydes of the formula I for the labeling of hydrocarbons, to a method for the detection of these benzaldehydes in the hydrocarbons, and to the hydrocarbons containing the above benzaldehydes as tracers.

Ring A can be annealed with a benzene ring,

R, R and R are each independently hydrogen, hydroxy, cyano, nitro, (C 1 -C 15) alkyl, (C 1 -C 15) alkoxy, or -NR ⁴ R ⁵ or -COOR ^{6 in} which:

R ⁴ is hydrogen or (C 1 -C 15) alkyl optionally substituted by phenyl, wherein the carbon chain continuity can be interrupted by 1 to 4 non-adjacent oxygen atoms,

^R5 is an optionally substituted phenyl group is a C1-15 alkyl, in which the continuity of the carbon chain is interrupted by 1 to 4 non-adjacent oxygen

2, meg, or a group of the formula -L-NX X wherein L is a C 2 -C 8 alkylene group and X ¹ and X ² are independently C 1 -C 6 alkyl or X and X together with the nitrogen atom between them are Forms a 5 or 6 membered saturated heterocyclic group which may even contain one oxygen atom as a heteroatom in the ring, and

R is hydrogen, a C 1 -C 15 alkyl group in which the chain continuity may be interrupted by 1 to 4 non-adjacent oxygen atoms, or a group -L-NxX ² wherein L, X ¹ and X ² are as defined above. specified.

US-A-5 145 573, US-A-5 182 372 and EP-A-499 845 disclose azo dyes which serve as tracers in mineral oils. Further, US-A-4 009 008 discloses a process for labeling mineral oils with bisazos dyes, wherein the colorant added to the mineral oil is visualized and wherein the mineral oil is adsorbed to the mineral oil to provide the other colored mineral constituents.

DE-A-3 608 215 and DE-A-3 724 757 describe benzopyran derivatives and their use in labeling systems.

Example 1 of DE-A-3 608 215 describes the reaction of 2,3-dimethylbenzopyrilium trichlorocinate (II) with 4- (dimethylamino) benzaldehyde in methanol. reaction to form the dye of formula (A).

The use of substituted anilines for the labeling of mineral oils is described in WO-A-11466/1994.

The object of the present invention was to find new tracers for the labeling of hydrocarbons. The new tracers should be readily available, highly soluble in hydrocarbons and easily detectable. In doing so, we need to be able to visualize very small amounts of tracer with a strong color reaction.

We have found that the above general image (I) • ·

Benzaldehyde derivatives are preferred markers for hydrocarbon labeling.

All alkyl and alkylene groups in the above definition of compounds of formula (I) may be linear or branched.

2

When X and X together with the nitrogen atom between them form a 5 or 6 membered saturated heterocyclic group which may even contain one oxygen atom as a heteroatom in the ring, this heterocyclic group may be, for example, 1-pyrrolidinyl, piperidino or morpholino.

R ¹ , R ⁴ , R ³ , R ⁴ , R ⁵ , R ⁶ , X ¹ and X ² may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, , isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may also be, for example, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isonyl, decyl, isodecyl, undecyl, , dodecyl, tridecyl, 3,5,5,7-tetramethyl-nonyl, isotridecyl, tetradecyl or pentadecyl (the above being the trivial names of the isooctyl, isononyl, isodecyl and isotridecyl groups obtained by oxosynthesis). derived from the names of alcohols - see Ullmann's

Encyclopedia of Industrial Chemistry, 5th edition, Vol

290-293. and pages 284 and 285 of Volume A10).

R ¹ , R ² and R ³ may also be for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy, tertiary pentyloxy, hexyloxy, 2-methylpentyloxy, heptyloxy, octyloxy, 2 ·· ··· ·

-ethylhexyloxy, isooctyloxy, nonyloxy, isonyloxy, decyloxy, isodecyloxy, undecyloxy, dodecyloxy, tridecyloxy, 3, 5,5,7-tetramethylnonyloxy, isotridecyloxy, tetradecyloxy or pentadecyloxy.

R ⁴ and R ⁵ may also be, for example, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2 and 3-methoxypropyl; , 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and

4-ethoxybutyl, 2- and 4-propoxybutyl, 2- and 4-butoxybutyl,

3,6-dioxa-heptyl, 3,6-, 3,7- and 4,7-dioxaoctyl, 4,8-, 3,7- and

4,7-dioxanonyl, 4,8-dioxa-decyl, 3,6,8-trioxa-decyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxa tridecyl, benzyl or 1 and 2-phenylethyl.

L can be, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene or -CH (CH ₃ ) -CH ₂ - and -CH (CH ₃ ) -CH (CH ₃ ) -.

Preferably, benzaldehyde derivatives of formula (I) wherein at least one of R ¹ -R ^{3 is a} group -NR ⁴ R ⁵ , wherein R ⁴ and R ⁵ are as defined above, are preferably used in the process of the invention. .

Particular preference is given to the use of benzaldehydes of formula (Ia) for the hydrocarbons, wherein R ¹ , R ² , R and R are as defined above.

Particularly suitable are benzaldehydes of formula Ia wherein R and R are independently hydrogen, hydroxy, C 1 -C 15 alkyl, C 1 -C 15 alkoxy, or a -COOR ⁶ group in which R ⁶ R ⁴ is hydrogen or C 1 -C 15 alkyl and R ⁵ is C 1 -C 15 alkyl as defined above.

Particularly preferred hydrocarbons are those benzaldehydes of formula (Ia) wherein R ⁴ and R ⁵ are independently C 1 -C 13 alkyl and R and R are hydrogen.

The present invention also relates to a method for detecting the presence of benzaldehydes of formula I in hydrocarbons by treating the hydrocarbon with an aqueous-alcoholic or alcoholic medium which is a protonic acid, the substituted benzopyrilium salts of formula II - a. wherein R ⁷ is C 1 -C 8 alkyl, phenyl, C 1 -C 5 alkoxy, or halogen, R is methyl

Or R and R together form a tetramethylene group, and ring B can be annealed with a benzene ring, and the compound is optionally C 1 -C 4 alkyl, 1-pyrrolidinyl, piperidino, morpholino, chloro or bromo, or is optionally further substituted by hydroxy, (C1-C4) alkoxy, (C1-C5) mono- or dialkylamino in the alkyl moiety, which itself may be substituted by chlorine or phenyl, and X represents any anion, and / or Indoles of formula III: wherein R ⁹ and R ¹⁰ are independently hydrogen, halo, a group -NR ⁴ R ⁵ , wherein R ⁴ and R ⁵ are as defined above, hydroxy, 1-8. alkyl, phenyl, or • ·

It represents at least one compound and optionally one zinc, aluminum or tin halide.

The indoles of the formula (III), in particular 2-phenylindole, are preferably used in the process of the invention.

Suitable anions X include, for example, halide, sulfate,

phosphate, [tetrachlorocinate (II)] or [tetrafluoroborate (III)] anion. The Benzaldehydes of formula (I), general (II) formula benzopyrilium salts; (III) of the general formula indoles generally known compounds.

In the context of the present invention, it is understood that benzaldehydes of formula (I) are added to the hydrocarbons in such a concentration that the color of the hydrocarbons is not or only slightly visible to the human eye, while the benzaldehydes of formula (I) they can be easily and visibly detected by detailed methods.

Finally, the present invention also relates to hydrocarbons containing one or more benzaldehyde (I) as a tracer.

In the context of the present invention, hydrocarbons are aliphatic or aromatic hydrocarbons which are normally liquid. These are mainly mineral oils such as fuels such as gasoline, kerosene or diesel oil, or oils such as fuel oil or motor oils.

The benzaldehydes of the formula I are particularly suitable for the designation of mineral oils which, for example, are required for tax purposes. In order to keep the cost of marking low, we need to try to use as little markup as possible on the mark.

The hydrocarbons are designated by the benzaldehydes of formula (I) either alone or in solution.

Suitable solvents for this purpose are organic solvents, preferably aromatic hydrocarbons such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a higher molecular weight aromatic compound commercially available as Shellsol AB (a product of Shell). In order to avoid the high viscosity of the resulting solution, the concentration of benzaldehydes of formula I in the solution is generally

5-80% by weight.

Other co-solvents may also be used to improve solubility such as 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, cresols such as ο-, m- or p-cresol, ketones such as diethyl ketone or cyclohexanone, lactones such as γ-butyrolactone, carbonates such as ethylene or propylene carbonate, phenols such as tertiary butyl or nonylphenol, esters such as dimethyl, die

ethyl, di (2-ethylhexyl) phthalate, ethyl, butyl or cyclohexyl acetate, acid amides such as N, N-dimethylformamide, N, N-diethylacetamide or N-methylpyrrolidinone or mixtures.

The benzaldehydes of formula (I) to be used in the process of the present invention are very easy to detect labeled hydrocarbons, even if they have a tracer concentration of about 10 ppm or less.

Preferably, the presence of the compounds of formula (I) used as tracers in the hydrocarbons is achieved by treating the hydrocarbon with an aqueous-alcoholic or alcoholic medium which comprises a pyrilium salt of formula (II) and / or an indole of formula (III) proton acid and optionally a zinc, aluminum or tin halide. When used in an aqueous-alcoholic medium, the weight ratio of water to alcohol is 0.5: 1 to 4: 1, but preferably about 1: 1. This causes a clear color change in the aqueous-alcoholic phase.

Examples of suitable alcohols are ethanol, propanol, isopropanol, 1-methoxypropan-2-ol, ethylene glycol, propylene glycol or 1,3-propanediol. Ethanol is preferred.

Suitable for the invention are mainly the so-called strong protonic acid, such as a proton, wherein pK _a <3.5. Examples of such acids include inorganic and organic acids such as perchloric acid, hydrogen iodide, hydrochloric acid gas, hydrobromic acid, hydrogen fluoride, sulfuric acid, nitric acid, phosphoric acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, methanesulfonic acid, acetic acid, dl chloroacetic acid or · bromoacetic acid. In some cases, it may be advantageous to buffer these acids by, for example, adding acetic acid.

In addition to o- or p-toluenesulfonic acid, inorganic acids are particularly preferred, and in particular hydrochloric or sulfuric acid.

Suitable zinc, aluminum and tin halides include, for example, zinc (II) chloride, zinc (II) bromide, aluminum (III) chloride, aluminum (III) bromide or tin tetrachloride. Zinc (II) chloride is particularly preferred.

The addition of a metal halide optionally to the solution, from 1 to 50 milliliters of an aqueous alcoholic or alcoholic solution of a benzopyrilium salt of the formula II and / or an indole of the formula III and a protonic acid, is generally sufficient according to the invention. shake with about 10 to 50 milliliters of hydrocarbon to obtain a color change. However, it is also possible to use only an aqueous alcoholic solution of the metal halide instead of the protonic acid solution since it is also acidic.

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

The inventive method has the great advantage of being able to use two different methods for the detection of benzaldehydes of formula (I). Therefore, the detection can be carried out with high reliability, even though there may be confounding factors (such as additives in diesel).

• »· · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Examples of the method of the invention:

General rule 1:

Benzaldehyde is always added to commercially available diesel at a concentration of 10 ppm. For this purpose, a 0.1 wt% solution of benzaldehyde in toluene is prepared and this solution is added to the diesel oil.

1-12 below. In Example 1, 2 ml of reagent solution are always added to milliliters of the so-called diesel oil and the reaction mixture is shaken for 5 minutes. Water (1 ml) was added and the reaction mixture was shaken for a further 5 minutes. The aqueous phase is as follows

Shows the color specified in Table 1.

Composition of reagent solution 1:

1% solution of indole in ethanol by weight 5 ml concentrated hydrochloric acid 5 ml zinc (II) chloride 5 g acetic acid 95 ml

Composition of reagent solution 2:

1% (w / w) solution of 2-methylindole in ethanol 5 ml concentrated hydrochloric acid 5 ml zinc (II) chloride 5 g acetic acid 95 ml

Composition of reagent solution 3:

1% (w / w) solution of 2-phenylindole in ethanol 5 ml concentrated hydrochloric acid 5 ml zinc (II) chloride 5 g acetic acid 95 ml

It is particularly advantageous to carry out the process according to the invention.

... ... .. ·

finally, filter the diesel oil through a Kieselgel filler before testing.

Table 1

Song aldehyde Reagent- solution Color 1 4- (dimethylamino) benzaldehyde 1 purple 2 4- (dimethylamino) benzaldehyde 2 violet 3 4- (dimethylamino) benzaldehyde 3 violet 4 2-hydroxy-4- (diethylamino) - benzaldehyde 1 orange 5 2-hydroxy-4- (diethylamino) - benzaldehyde 2 red-violet 6 2-hydroxy-4- (diethylamino) - benzaldehyde 3 purple 7 2-hydroxy-4-morpholino-benzaldehyde 1 orange 8 2-hydroxy-4-morpholino-benzaldehyde 2 red-violet 9 2-hydroxy-4-morpholino-benzaldehyde 3 purple 10 2-acetoxy-4- (dimethylamino) - benzaldehyde 1 red-violet 11 2-acetoxy-4- (dimethylamino) - benzaldehyde 2 Blue-violet 12 2-acetoxy-4- (dimethylamino) - benzaldehyde 3 Blue-violet

The process of the present invention may be similarly advantageously carried out using the benzaldehydes listed in Table 2 below as tracers.

«• e -» * * »» * ·

Table 2

Song aldehyde 13 4- (diethylamino) benzaldehyde 14 4- (dibenzylamino) benzaldehyde 15 4- (1-pyrrolidinyl) -benzaldehyde 16 4-piperidino-benzaldehyde 17 4- [N- (2-cyanoethyl) methylamino] benzaldehyde 18 2-hydroxy-4- (dimethylamino) benzaldehyde 19 2-hydroxy-4- (dibenzylamino) benzaldehyde 20 2-methoxy-4- (diethylamino) benzaldehyde

. general prescription

Benzaldehyde is always added to commercially available diesel at a concentration of 10 ppm. For this purpose, a 0.1 wt% solution of benzaldehyde in toluene is prepared and this solution is added to the diesel oil.

21 to 30 below. In Example 1, 2 ml of reagent solution 4 are always added to milliliters of the so-called diesel oil and the reaction mixture is refluxed for 5 minutes. Then, 1 ml of a 1: 1 mixture of water and ethanol (v / v) was added to the reaction mixture and the reaction mixture was shaken for 5 minutes. The aqueous phase shows the color shown in Table 3 below.

Composition of reagent solution 4:

Aqueous solution of benzopyrilium salt of formula Ha in 5% by weight of concentrated hydrochloric acid 25 ml of acetic acid

225 ml • · • a · ·

Table 3

Song aldehyde <2 Color 21 4- (dimethylamino) benzaldehyde phenyl blue 22 4- (dimethylamino) benzaldehyde methyl blue 23 2-acetoxy-4- (dimethylamino) - benzaldehyde phenyl blue 24 2-acetoxy-4- (dimethylamino) - benzaldehyde H blue 25 2-hydroxy-4- (diethylamino) benzaldehyde methyl blue 26 2-hydroxy-4-morpholino-benzaldehyde methyl blue 27 2-hydroxy-4-morpholino-benzaldehyde H blue 28 4-hydroxybenzaldehyde methyl red-violet 29 4-methoxybenzaldehyde methyl red-violet 30 2,4-dimethoxybenzaldehyde methyl violet

The process of the present invention can be similarly advantageously carried out by replacing the benzopyrilium salt of formula IIa in reagent solution 4 with a compound of formula IV.

Claims (5)

Claims 1. Benzaldehydes of formula I - wherein ring A may be annealed with a benzene ring, R ¹ , R ² and R ³ are each independently hydrogen, hydroxy, cyano, nitro, C 1 -C 15 alkyl, C 1 -C 15 alkoxy, or a group -NR R or -COOR formulas R ⁴ is hydrogen or (C 1 -C 15) alkyl optionally substituted by phenyl, wherein the carbon chain continuity can be interrupted by 1 to 4 non-adjacent oxygen atoms, ^R5 is an optionally substituted phenyl group is a C1-15 alkyl, in which the continuity of the carbon chain may be interrupted by from 1 to 4 non-adjacent oxygen atoms, or a -L-NX * X "is a group of formula wherein L is C 2-8 alkylene and X ¹ and X ² are each independently C 1 -C 6 alkyl, or X and X together with the nitrogen atom between them form a 5 or 6 membered saturated heterocyclic group which may even contain one oxygen atom in the ring, and R is hydrogen, a C 1 -C 15 alkyl group in which the chain continuity may be interrupted by 1 to 4 non-adjacent oxygen atoms, or a group of the formula -L-NX ^ ² wherein L, X ¹ and X ² are as defined above - use as a tracer for the labeling of hydrocarbons. • · 2. The use of benzaldehydes of general formula I according to claim 1 (I), characterized in that the tracer of benzaldehydes of general formula (Ia) are used, wherein R ^1, R ^2, R ⁴ and R ^{5 are} as defined in claim 1. Use of benzaldehydes of formula I or Ia according to claim 1 or 2, characterized in that the benzaldehydes of formula I or Ia in which R ¹ and R ² independently represent hydrogen, hydroxy, C 1 -C 15 alkyl, C 1 -C 15 alkoxy, or a -COOR ⁶ group in which R ⁶ is as defined in claim 1, R ⁴ is hydrogen or C 1 -C 15 alkyl, and R ⁵ is C1-C15 alkyl. 4. A method for detecting the presence of benzaldehydes of formula I according to claim 1, wherein the hydrocarbon is treated with an aqueous-alcoholic or alcoholic medium which is a protonic acid, the substituted benzopyrilium salts of formula II - wherein R ⁷ is C 1 -C 8 alkyl, phenyl, C 1 -C 5 alkoxy or halogen, R ⁸ is methyl, or R and R together form a tetramethylene group, and ring B may be anellated with a benzene ring, and optionally C 1 -C 4 alkyl, 1-pyrrolidinyl, piperidino, morpholino, chloro or bromo, or optionally substituted in the 7-position of the ring with hydroxy, C 1 -C 4 alkoxy, in the alkyl moiety It may also be substituted by a C 1 -C 5 mono- or dialkylamino group which may itself be substituted by a chlorine atom or a phenyl group and X represents any anion - and / or indoles of general formula (III) - in which R and R are independently hydrogen, halogen at least one compound of the formula -NR ⁴ R ⁵ wherein R ⁴ and R ^{5 are} as defined in claim 1, being hydroxy, C 1 -C 8 alkyl, phenyl or C 1 -C 5 alkoxy, and optionally containing a zinc, aluminum or tin halide. Hydrocarbons, characterized in that they contain one or more benzaldehydes of the formula (I) according to claim 1 as a tracer. FLI