ES2877166T3 - Use of triarylbenzene derivatives as marking tracers for fuels and liquid fuels, fuels and liquid fuels containing such derivatives and corresponding processes - Google Patents

Abstract

Use as a marking tracer for fuels and liquid fuels of at least one compound of Formula I: in which: - the benzene ring A is optionally substituted in at least one of the 2, 4 or 6 positions by: - an alkyl radical , linear, branched or cyclic, from C1-C18, optionally substituted by at least one halogen and/or optionally interrupted by at least one oxygen; or - a C1-C18 linear, branched or cyclic alkoxy radical, optionally substituted by at least one halogen and/or optionally interrupted by at least one oxygen; or - a C2-C18 linear, branched or cyclic alkenyl radical, optionally substituted by at least one halogen and/or optionally interrupted by at least one oxygen; - the benzene rings B, C and D are substituted, independently of each other, in at least one ortho, meta or para position with respect to the benzene ring A by: - a linear, branched or cyclic C1 alkyl radical -C18, optionally substituted by at least one halogen and/or optionally interrupted by at least one oxygen; or - a C1-C18 linear, branched or cyclic alkoxy radical, optionally substituted by at least one halogen and/or optionally interrupted by at least one oxygen; or - a C2-C18 linear, branched or cyclic alkenyl radical, optionally substituted by at least one halogen and/or optionally interrupted by at least one oxygen; or - a halogen; at least one benzene ring B, C and D which may additionally contain a 5-7 membered aliphatic ring coupled to it, for example a 6 membered ring, with the proviso that when the benzene ring A is not substitute and the benzene rings B, C and D are each replaced by a methyl, the latter will not be in position with respect to the benzene ring A.

Description

DESCRIPTION

Use of triarylbenzene derivatives as marking tracers for fuels and liquid fuels, fuels and liquid fuels containing such derivatives and corresponding processes

[0001] The present invention relates to the use of triarylbenzene derivatives as marking tracers for fuels and liquid fuels; to fuels and liquid fuels containing such derivatives; to a procedure for marking fuels and liquid fuels for such derivatives; and a procedure for determining whether fuels or liquid fuels initially containing these tracers have been counterfeit, illegally used, or stolen.

[0002] The marking of fuels and liquid fuels with different types of chemical markers is widely known in the state of the art. Compounds have been used for this purpose, as well as numerous analytical techniques for the detection of markers (eg gas chromatography coupled to mass spectrometry). An important application is to mark combustible fuels according to their tax rate. Deliberate removal of the tracer for illegal purposes is an important issue. Since tracers until now had dyes, the "removal methods" were called "bleaching methods." These methods are physical (for example: adsorption on carbon or on silica) or chemical (for example: acid or basic treatment). Consequently, these markers must be resistant to such removal methods, fully compatible with fuels and liquid fuels, and identifiable by an appropriate analytical method.

[0003] Fraud in relation to fuels or liquid fuels encompasses different behaviors: counterfeiting by laundering or adulteration, illegal use, smuggling and theft. Counterfeiting by laundering refers to the transformation of a fuel or liquid fuel with a low tax rate on fuel or liquid fuel with a higher tax rate, for example - in France - the transformation of fuel for domestic use into diesel. Counterfeiting by adulteration refers to the dilution of a fuel or liquid fuel with a high tax rate in fuel with a fuel or liquid fuel with a low tax rate. Illegal use refers to the illegal use of a fuel or liquid fuel with a low tax rate instead of a fuel or liquid fuel with a higher tax rate. Smuggling refers to the purchase of a fuel or liquid fuel with a low tax rate in one country to resell it in another country where taxes are higher.

[0004] WO2012 / 153132 A1 describes aromatic organic labels substituted by at least one bromine and / or one fluorine atom, and / or one or more fluoroalkyl groups. Combustion of fuels labeled with such compounds can produce hydrogen bromide and / or hydrogen fluoride in the combustion gases. Hydrogen bromide and fluoride are known to be especially corrosive to engines. Hydrogen fluoride is well known to be highly toxic to people and the environment.

[0005] WO2014 / 008164 describes aryl and tritylated alkyl ethers as tracers for marking hydrocarbons. Such tracers do not exhibit good resistance to the aforementioned removal methods.

[0006] US 5981 283 describes the use of a wide variety of organic compounds for the marking of petroleum products, including 1,3,5-triphenylbenzene. This tracer compound does not exhibit good resistance to the above-mentioned removal methods.

[0007] US 7858373 describes the use of a variety of organic compounds for use in marking liquid fuels such as hydrocarbons and oils. Combinations of markers can be used as digital marking systems, with the ratio of the concentration of each marker forming a code for the marked product.

Therefore, there is still a need for supplementary chemical markers compatible with fuels and liquid fuels, detectable in such a complex medium and resistant to physical and chemical bleaching methods, at least to the physical method of activated carbon bleaching. and / or silica.

[0009] Surprisingly, certain triarylbenzenes have been found to be especially effective for marking fuels and liquid fuels. Furthermore, these triarylbenzenes have been shown to be particularly resistant to chemical and physical bleaching attempts. On the other hand, most of these triarylbenzenes only contain carbon and hydrogen and the combustion of these compounds used as markers only produces carbon dioxide and water.

Therefore, the present invention aims, first of all, the use as marking tracer of fuels and liquid fuels of at least one compound of Formula I:

in which:

- the benzene ring A is optionally substituted in at least one of the 2, 4 or 6 positions by:

• a C1-C18 linear, branched or cyclic alkyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

• a C1-C18 linear, branched or cyclic alkoxy radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

• a C2-C18 linear, branched or cyclic alkenyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen;

- the benzene rings B, C and D are substituted, independently of each other, in at least the ortho, meta or para to the benzene ring A position:

• a C1-C18 linear, branched or cyclic alkyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

• a C1-C18 linear, branched or cyclic alkoxy radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

• a C2-C18 linear, branched or cyclic alkenyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or

• a halogen;

where at least one benzene ring B, C and D may further contain a 5-7 membered aliphatic ring coupled to it, for example a 6 membered ring,

Provided that when benzene ring A is not substituted and benzene rings B, C and D are each substituted by a methyl, the latter will not be in position with respect to benzene ring A.

[0011] It should be noted that, in Formula 1, every atom can be replaced by one of its isotopes.

[0012] Preferably, benzene ring A is not substituted, or is substituted by C1-C18 alkoxy.

[0013] Preferably, benzene rings B, C and D are replaced by:

- a linear, branched or cyclic alkyl radical of C1-C18, especially C1-C12, in particular C1-C6, optionally substituted by at least one halogen; or

- at least one halogen.

[0014] A halogen that is included in the definition of Formula I can be F, Cl, Br and I, and in particular F, Cl and Br.

[0015] The compound of Formula I can be chosen especially from:

[0016] Particularly preferably, the compound of Formula I is:

[0017] Another object of the invention is a fuel or liquid fuel that contains as marking tracer at least one compound of Formula I.

[0018] As fuel or liquid fuel, the following can be mentioned:

- Fuels or liquid fuels obtained from oil, among which we can mention gasoline, diesel, fuel for domestic use, kerosene, lampante oil;

- fuels or liquid fuels obtained from plants such as biofuels, including vegetable oils, ethanol, butanol, ethyl tert-butyl ether (ETBE), fatty acid methyl esters.

[0019] Compounds of Formula I can be prepared by palladium catalyzed Suzuki coupling between a 1,3,5-trihalogenoarene with substituents at the 2, 4 or 6 positions and three equivalents of an arylboronic acid in the presence of a mineral base :

[0020] Compounds of Formula I without substituents on the benzene A ring, can also be prepared by cytotrimerization of arylmethyl ketones, according to:

[0021] The reaction takes place between 80 and 150 ° C in the presence of catalysts or dehydrating agents. The catalysts are Bronsted or Lewis acids. The use of arenesulfonic acids is well described in the literature. In particular the use of a catalytic amount of 4-toluenesulfonic acid monohydrate is described in Zhao, Y .; Li, J .; Li, C .; Yin, K .; Ye, D .; Jia, X. Green Chem. 2010, 12, 1370.

The compound of Formula I is added to the fuel or liquid fuel at a rate of 0.01 to 500 mg / L, in particular at a rate of 0.02 to 20 mg / L, and more particularly at a rate of 0.1 at 5 mg / L.

[0023] The invention also has as its object a process for marking fuels or liquid fuels, characterized in that a solution at 0.1-40% by weight of the compound of Formula I is prepared in a solvent or a mixture of solvents and that said solution is injected into the fuel or liquid fuel, for example in line in an oil pipeline or in the loading arm of a tanker truck, or also in a tank to obtain the target concentration of the marker in the fuel or fuel liquid.

[0024] Preferably, a 0.2-20% by weight solution of the compound of Formula I is prepared in the solvent or solvent mixture.

[0025] The solvent (s) can be chosen from aromatic solvents such as toluene, ethylbenzene, xylenes, mesitylene, 1,2,4-trimethylbenzene, cumene, p-cymene, aromatic hydrocarbons (for example Shellsol® A100, Solvarex® 10, Solvesso® 200); among aliphatic solvents such as pentane, hexanes, cyclohexane, heptanes, 2,2,4-trimethylpentane, white gasoline, kerosene, isoparaffins, paraffins; among oxygenated and / or nitrogenous solvents such as ketones, ethers, esters, lactones, phenols, amides, lactams; or between halogenated solvents such as chlorobenzene, 1,2-dichlorobenzene, a, a, a-trifluorotoluene.

[0026] The invention also aims at a method for determining whether fuels or liquid fuels have been counterfeited by bleaching, characterized by the fact that a sample of the fuel or liquid fuel suspected of having been counterfeited is taken and is analyzes to determine if the concentration of the compound of Formula I in said sample is lower than the initial concentration, and, if so, it is deduced that the sample has been falsified by bleaching.

The invention also aims at a method for determining whether fuels or liquid fuels have been falsified by adulteration, or if they have been used illegally or have been smuggled or stolen, characterized by the fact that they are takes a sample of the fuel or liquid fuel suspected of having been counterfeit or illegally used or has been smuggled or stolen and is tested to determine whether the Formula I compound is present in the sample, and If so, it follows that the sample has been falsified or used illegally or has been smuggled or stolen.

[0028] It should be noted here that the marker (s) according to the invention can be used individually or in combination with other markers.

[0029] Fuels or liquid fuels labeled by one or more compounds of Formula I can be analyzed qualitatively or quantitatively, for example, by the following methods: gas chromatography coupled to a flame ionization detector or a mass spectrometer; High performance liquid chromatography coupled to a diode array detector or mass spectrometer.

The following Examples illustrate the present invention without however limiting its scope. In these Examples, the percentages are by weight unless otherwise indicated.

[0031] The following tests of physical and chemical removal of the markers have been carried out on the compounds of Examples 1 (reference), 2 to 18 (of the invention) and 19 and 20 (comparative).

Physical elimination test

[0032] In a test tube, to 10 mL of type B0 diesel according to EN 590 standard containing 10 mg / L of chemical marker, a quantity - specified below - of solid eliminating agent was added: silica ¹ , activated carbon ² ; alumina ³ .

¹ 0.060-0.200mm, 40A, Acros 241660010

² Comelt Carbosorb 10A

³ Sigma-Aldrich 11028

[0033] The tube was shaken using a 300 strokes / min linear shaker for 10 min.

[0034] The liquid was then filtered through a 0.2 µm polytetrafluoroethylene (PTFE) membrane and analyzed by GC / FID.

Column ZB-50 15 m x 0.25 mm x 0.25 ^ m ID.

Helium P = 90kPa

Flow of 50 mL / min.

Injector 280 ° C

300 ° C detector

Oven: 100 ° C to 320 ° C at 20 ° C / min and then 320 ° C for 19 min.

Injected volume: 2 | jL.

Chemical removal test

[0035] In a test tube, 10 mL of chemical removal agent were added to 10 mL of type B0 diesel according to EN 590 standard containing 10 mg / L of chemical marker: H ² SO ⁴ , HNO ³ , NaOH, NaClO, HCl at the indicated concentrations.

[0036] The tube was shaken using a 300 strokes / min linear shaker for 10 min. After a few minutes of standing, the liquid constituting the upper phase was removed and then filtered through a 0.45 µm polytetrafluoroethylene (PTFE) membrane and analyzed by GC / FID. The analysis conditions are those indicated above for the physical elimination test.

The gas oil containing the compound of Examples 1 to 18 of the concentration of 10 mg / L was subjected to the physical and chemical removal tests described above. The concentration of each compound, measured in the gas oil after the elimination treatment, is indicated in Tables 1 to 18 respectively as a percentage of the concentration measured before the elimination treatment.

Example 1 (reference): 1,3,5-T ris (4-methylphenyl) benzene

[0038]

[0039] A mixture of 134.2 g of 4'-methylacetophenone and 19 g of 4-toluenesulfonic acid monohydrate was heated to 140 ° C while stirring. The water was removed by distillation to reach temperature and then during the reaction. The temperature of 140 ° C was maintained for 24 h.

[0040] After cooling the reaction mixture to room temperature, toluene was added to dissolve the mass. The organic solution was then washed 3 times with water and then dried over magnesium sulfate. The solvent was removed by vacuum distillation.

[0041] 92 g of 1,3,5-Tris (4-methylphenyl) benzene were obtained. Purification by silica gel chromatography (cyclohexane / ethyl acetate: 99/1) followed by recrystallization from ethanol resulted in a beige crystalline powder.

T l 1

Example 2 (of the invention): 1,3,5-Tris (4-isobutylphenyl) benzene

[0042]

[0043] The title compound was prepared according to the operating sequence of Example 1 except that the initial mixture was a mixture of 176.3 g of 4'-isobutylacetophenone and 19 g of 4-toluenesulfonic acid monohydrate.

[0044] 126 g of a very viscous brown liquid were obtained containing 68% (m / m) of 1,3,5-tris (4-isobutylphenyl) benzene.

T l 2

Example 3 (of the invention): 1,3,5-Tris (4-butylphenyl) benzene

[0045]

[0046] The title compound was prepared according to the operating sequence of Example 1, except that the initial mixture was a mixture of 10 g of 4'-butylactophonone and 1.1 g of 4-toluenesulfonic acid monohydrate.

[0047] 10.1 g of 1,3,5-tris (4-butylphenyl) benzene were obtained in the form of a very viscous brown liquid.

Example 4 (of the invention): 1,3,5-Tris (4-tert-butylphenyl) benzene

[0048]

[0049] 1.23 g of 1,3,5-triphenylbenzene were suspended in 10 mL of dichloromethane and 1.5 mL of 2-chloro-2-methylpropane. Then 25 mg of ferric chloride were added. After a few minutes, added the water and dichloromethane while stirring. The organic solution was then washed twice with a 10% aqueous sodium carbonate solution, dried over magnesium sulfate and evaporated in vacuo. 1.88 g of 1,3,5-Tris (4-tert-butylphenyl) benzene were obtained. After recrystallization from toluene, a white crystalline product resulted.

T l 4

Example 5 (of the invention): 1,3,5-Tris (4-ethylphenyl) benzene

[0050]

[0051] The title compound was prepared according to the operating sequence of Example 1 except that the initial mixture was a mixture of 10 g of 4'-ethylacetophenone and 1.3 g of 4-toluenesulfonic acid monohydrate.

[0052] 7.3 g of 1,3,5-tris (4-ethylphenyl) benzene were obtained in the form of a very viscous brown liquid.

T l

Example 6 (of the invention): 1,3,5-Tris (4-fluorophenyl) benzene

[0053]

[0054] Under argon atmosphere, a mixture of 630 mg of 1,3,5-tribromobenzene, 1.007 g of 4-fluorophenylboronic acid, 15 mg of palladium acetate and 52 mg of triphenylphosphine in 4 mL of solution was heated to reflux. 2M aqueous sodium carbonate and 13 mL of 1-propanol while stirring for 3 h.

[0055] Next, 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4% aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and then evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.53 g of 1,3,5-tris (4-fluorophenyl) benzene as a grayish-white crystalline powder.

T l

Example 7 (of the invention): 1,3,5-Tris (4-chlorophenyl) benzene

[0056]

[0057] 1,3,5-tris (4-chlorophenyl) benzene was prepared according to the operating sequence of Example 1 replacing 4'-methylacetophenone with 4'-chloroacetophenone. The crude product was recrystallized from ethanol. 36.8 g of yellowish white crystals were obtained.

Table 7

Example 8 (of the invention): 1,3,5-Tris (4-bromophenyl) benzene

[0058]

[0059] 1,3,5-Tris (4-bromophenyl) benzene was prepared according to the operating sequence of Example 1 replacing 4'-methylacetophenone with 4'-bromoacetophenone. The crude product was recrystallized from toluene. 54.3 g of yellowish white crystals were obtained.

Table 8

Example 9 (of the invention): 1-Dodecyloxy-2,4,6-tris (4-fluorophenyl) benzene

[0060]

[0061] A mixture of 12.8 g of 2,4,6-tribromophenol, 9.85 g of 1-bromododecane and 10.35 g of potassium carbonate in 25 mL of N-ethylpyrrolidone was heated to 115 ° C while stirring for 2 h. The mixture was then poured into cold water. 16% hydrochloric acid was added until pH <2. Then the product was extracted with cyclohexane. The organic solution was then washed with water, dried over potassium carbonate and then evaporated in vacuo to give 18.6 g of 1-dodcyloxy-2,4,6-tribromobenzene.

[0062] Under argon atmosphere, a mixture of 998 mg of 1-dodecyloxy-2,4,6-tribromobenzene, 1.007 g of 4-fluorophenylboronic acid, 15 mg of palladium acetate and 52 mg of triphenylphosphine in 4 mL of 2 M aqueous sodium carbonate solution and 13 mL of 1-propanol while stirring for 3 h.

[0063] Then, 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4% aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.69 g of 1-dodecyloxy-2,4,6-tris (4-fluorophenyl) benzene as a white crystalline powder.

T l

Example 10 (of the invention): 1-Octyloxy-2,4,6-tris (4-fluorophenyl) benzene

[0064]

[0065] 1-Octyloxy-2,4,6-tribromobenzene was prepared according to the procedure of Example 9 replacing 1-bromododecane with 1-bromooctane.

[0066] Under argon, a mixture of 1.33 g of 1-octyloxy-2,4,6-tribromobenzene, 1.51 g of 4-fluorophenylboronic acid, 99 mg of palladium acetate and 297 mg of triphenylphosphine in 6 mL of 2M aqueous sodium carbonate solution and 20 mL of 1-propanol while stirring for 2 h.

[0067] Next, 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4 % aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.4 g of 1-Octyloxy-2,4,6-tris (4-fluorophenyl) benzene as a white crystalline powder.

T l 1

Example 11 (of the invention): 1-Butoxy-2,4,6-tris (4-fluorophenyl) benzene

[0068]

[0069] 1-Butoxy-2,4,6-tribromobenzene was prepared according to the procedure of Example 9 replacing 1-bromododecane with 1-bromobutane.

[0070] Under argon atmosphere, a mixture of 774 mg of 1-butoxy-2,4,6-tribromobenzene, 1.007 g of 4-fluorophenylboronic acid, 15 mg of palladium acetate and 52 mg of triphenylphosphine in 4 mL of a 2 M aqueous sodium carbonate solution and 13 mL of 1-propanol while stirring for 2 h.

[0071] 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4% aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and then evaporated in vacuo.

The crude product was recrystallized from ethanol to give 0.52 g of 1-Butoxy-2,4,6-tris (4-fluorophenyl) benzene as a white crystalline powder.

T l 11

Example 12 (of the invention): 1-Dodecyloxy-2,4,6-tris (3,4-difluorophenyl) -benzene

[0072]

[0073] Under argon atmosphere, a mixture of 998 mg of 1-dodcyloxy-2,4,6-tribromobenzene (see Example 9), 1.14 g of 3,4-difluorophenylboronic acid, 66 mg of palladium acetate and 200 mg of triphenylphosphine in 4 mL of 2M aqueous sodium carbonate solution and 13 mL of 1-propanol while stirring for 2 h.

[0074] 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4 % aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and then evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.48 g of 1-dodecyloxy-2,4,6-tris (3,4-difluorophenyl) benzene as a white crystalline powder.

T l 12

Example 13 (of the invention): 1- Octyloxy-2,4,6-tris (3,4-difluorophenyl) -benzene

[0075]

[0076] Under argon atmosphere, a mixture of 886 mg of 1-octyloxy-2,4,6-tribromobenzene (see Example 10), 1.14 g of 3,4-difluorophenylboronic acid, 15 mg of acetate was heated to reflux of palladium and 52 mg of triphenylphosphine in 4 mL of 2M aqueous sodium carbonate solution and 13 mL of 1-propanol while stirring for 3 h.

[0077] 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4% aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and then evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.83 g of 1-octyloxy-2,4,6-tris (3,4-difluorophenyl) benzene as a grayish crystalline powder.

T l 1

Example 14 (of the invention): 1-Dodecyloxy-2,4,6-tris (4-methylphenyl) benzene

[0078]

[0079] Under argon atmosphere, a mixture of 998 mg of 1-dodecyloxy-2,4,6-tribromobenzene (see Example 9), 979 mg of 4-tolylboronic acid, 66 mg of palladium acetate and 199 mg of triphenylphosphine in 4 mL of 2M aqueous sodium carbonate solution and 14 mL of 1-propanol while stirring for 4 h. Then 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4% aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and then evaporated in vacuo. The crude product was recrystallized from ethanol to obtain 0.59 g of 1-octyloxy-2,4,6-tris (4-methylphenyl) benzene as a white crystalline powder.

Table 14

Example 15 (of the invention): 1 -octyloxy-2,4,6-tris (4-methylphenyl) benzene

[0080]

[0081] Under argon atmosphere, a mixture of 886 mg of 1-octyloxy-2,4,6-tribromobenzene (see Example 10), 979 mg of 4-tolylboronic acid, 66 mg of palladium acetate and 199 mg of triphenylphosphine in 4 mL of 2M aqueous sodium carbonate solution and 14 mL of 1-propanol while stirring for 2 h.

[0082] 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4% aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and then evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.58 g of 1-octyloxy-2,4,6-tris (4-methylphenyl) benzene as a white crystalline powder.

T l 1

Example 16 (of the invention): 1-Butoxy-2,4,6-tris (4-methylphenyl) benzene

[0083]

[0084] Under argon atmosphere, a mixture of 182 mg of 1-butoxy-2,4,6-tribromobenzene (see Example 11), 230 mg of 4-tolylboronic acid, 15 mg of palladium acetate and 47 mg of triphenylphosphine in 1 mL of 2M aqueous sodium carbonate solution and 3.5 mL of 1-propanol while stirring for 2 h.

[0085] Next, 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4% aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and then evaporated in vacuo. The crude product was recrystallized from ethanol to give 0.15 g of 1-octyloxy-2,4,6-tris (4-methylphenyl) benzene as a white crystalline powder.

__________ Table 16__________

For 10 mL of marked diesel:

Example 17 (of the invention) -: 1-Dodecyloxy-2,4,6-tris (3-trifluoromethyl-phenyl) benzene

[0086]

[0087] Under argon atmosphere, a mixture of 998 mg of 1-dodecyloxy-2,4,6-tribromobenzene (see Example 9), 1.37 g of 3-trifluoromethylphenyloboronic acid, 66 mg of acetate of palladium and 199 mg of triphenylphosphine in 4 mL of 2M aqueous sodium carbonate solution and 14 mL of 1-propanol while stirring for 3 h.

[0088] 20 mL of water were added. The product was extracted twice with ethyl acetate. The organic solution was then washed with 4% aqueous sodium bicarbonate solution and saturated brine, dried over magnesium sulfate, filtered over Hyflo®, and then evaporated in vacuo. 1.62 g of 1-dodecyloxy-2,4,6-tris (3-trifluoromethylphenyl) benzene as a brownish oil.

Example 18 (of the invention) -: 1,3,5-Tris (2-methylphenyl) benzene

[0089]

[0090] The product is available from Sigma-Aldrich ( ref. 764671).

T l 1

Example 19 (comparative): ((3- (sec-butyl) -4- (decyloxy) phenyl) -methanetriyl) tribenzene

[0091]

[0092] Patent application WO2014 / 008164 especially describes ((3- (sec-butyl) -4- (decyloxy) phenyl) -methanetriyl) tribenzene, marketed under the name Accutrace S10®.

[0093] Gas oil containing ((3- (sec-butyl) -4- (decyloxy) phenyl) -methanetriyl) tribenzene in the concentration of 10 mg / L was subjected to the physical and chemical removal tests described above. The concentration of the compound measured in the gas oil after the elimination treatment is indicated in Table 19 as the percentage of the concentration measured before the elimination treatment.

[0094] The compound of Example 2 is clearly more resistant to treatment by silica than the compound of Comparative Example 19. Furthermore, the marker of Comparative Example 19 is totally eliminated by nitric acid when the compound of Example 2 exhibits a very good resistance to this chemical agent.

Example 20 (comparative): 1,3,5-triphenylbenzene (TPB)

[0095] The product is available from Sigma-Aldrich ( ref. T82007).

T l 2

[0096] The compound of Example 2 is clearly more resistant to treatment by activated carbon than TPB. Furthermore, the compound of Example 2 is superior to TPB for resistance to treatment by silica.

Example 21: Dirt test of fuel injection pipes according to CEC F-23-01 standard

[0097] This test was carried out on type B0 diesel according to EN 590 on the one hand without a marker and on the other with the marker from Example 2 added at a rate of 6.8 mg / L.

[0098] The average percentage reduction of the air flow in the injector at 0.1 mm needle lift is 70.8 for fuel without marker and 69.5 for fuel with marker. The addition of the marker therefore has no significant influence on the dirtiness of the injection lines.

Claims (11)

1. Use as a marking tracer for fuels and liquid fuels of at least one compound of Formula I:

in which: - the benzene ring A is optionally replaced in at least one of the 2, 4 or 6 positions by: • a C1-C18 linear, branched or cyclic alkyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or • a C1-C18 linear, branched or cyclic alkoxy radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or • a C2-C18 linear, branched or cyclic alkenyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; - the benzene rings B, C and D are substituted, independently of each other, in at least the ortho, meta or para to the benzene ring A position: • a C1-C18 linear, branched or cyclic alkyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or • a C1-C18 linear, branched or cyclic alkoxy radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or • a C2-C18 linear, branched or cyclic alkenyl radical, optionally substituted by at least one halogen and / or optionally interrupted by at least one oxygen; or • a halogen; at least one benzene ring B, C and D which may also contain a 5-7 membered aliphatic ring coupled to this, for example a 6 membered ring, Provided that when benzene ring A is not substituted and benzene rings B, C and D are each substituted by a methyl, the latter will not be in position with respect to benzene ring A. 2. Use according to claim 1, characterized in that the benzene ring A is not substituted, or is substituted by C1-C18 alkoxy. Use according to one of claims 1 and 2, characterized in that the benzene rings B, C and D are replaced by: - a linear, branched or cyclic alkyl radical of C1-C18, particularly C1-C12, in particular C1-C6, optionally substituted by at least one halogen; or - at least one halogen. Use according to one of claims 1 to 3, characterized in that a halogen included in the definition of Formula I is F, Cl, Br and I, and in particular F, Cl and Br. Use according to one of claims 1 to 4, characterized in that the compound of Formula I is selected from:

in particular:

6. Fuel or liquid fuel containing at least one compound of Formula I as defined in one of claims 1 to 5, characterized in that the compound of Formula I is adds to fuel or liquid fuel at a rate of 0.01 to 500 mg / L, in particular at a rate of 0.02 to 20 mg / L, and particularly at a rate of 0.1 to 5 mg / L. 7. Process for marking fuels or liquid fuels, characterized in that a 0.1-40% solution by weight of the compound of Formula I is prepared as defined in one of claims 1 to 5 in a solvent or a mixture of solvents, and that said solution is injected into the fuel or liquid fuel, for example in line in an oil pipeline or in the loading arm of a tank truck, or also in a tank to obtain the expected concentration marker in fuel or liquid fuel. 8. Process according to claim 7, characterized in that a 0.2% by weight solution of the compound of Formula I is prepared in the solvent or solvent mixture. 9. Process according to one of claims 7 and 8, characterized in that the solvent (s) are chosen from aromatic solvents such as toluene, ethylbenzene, xylenes, mesitylene, 1,2,4-trimethylbenzene , cumene, p-cymene, aromatic hydrocarbons (for example Shellsol® A100, Solvarex® 10, Solvesso® 200); among aliphatic solvents such as pentane, hexanes, cyclohexane, heptanes, 2,2,4-trimethylpentane, white gasoline, kerosene, isoparaffins, paraffins; among oxygenated and / or nitrogenous solvents such as ketones, ethers, esters, lactones, phenols, amides, lactams; or among halogenated solvents such as chlorobenzene, 1,2-dichlorobenzene, a, a, atrifluorotoluene. 10. Procedure to determine whether fuels or liquid fuels have been counterfeited by bleaching, characterized by the fact that a sample of the fuel or liquid fuel suspected of having been counterfeited is taken and analyzed to determine whether the concentration of compound of Formula I as defined in one of claims 1 to 5 in said sample is lower than the initial concentration, and, if so, it follows that the sample has been falsified by bleaching. 11. Procedure to determine if fuels or liquid fuels have been falsified through adulteration, or have been used illegally or have been the object of smuggling or theft, characterized by the fact that a sample of the fuel or liquid fuel is taken from the that it is suspected that it has been falsified or used illegally or has been the object of contraband or theft, and that is analyzed to determine if the compound of Formula I as defined in one of the claims 1 to 5 is present in said sample, and, if so, it follows that the sample has been falsified or used illegally or that it has been smuggled or stolen.