HUT76518A - Use of leucotriarylmethanes for marking hydrocarbons - Google Patents

Description

Use of Leucotiaryryl Methane for Hydrocarbon Marking

BASF AKTIENGESELLSCHAFT, LUDWIGSHAFEN, DE

inventors:

SCHLÖSSER Ulrike, LUDWIGSHAFEN, DE

BECK Karín Heidrun, LUDWIGSHAFEN, DE

RAULFS Friedrich-Wilhelm, LUDWIGSHAFEN, DE

GESSNER Thomas, HEIDELBERG, DE

MAYER Udo, FRANKENTHAL, DE

Date of filing: 16.06.1995

Priority: 27.06.1994, P 44 22 336.6, DE

International Application Number: PCT / EP95 / 02341

International Publication Number: WO 96/00272

The present invention relates to leucotrylmethane of formula (I): wherein

Z is optionally substituted phenyl, optionally substituted naphthyl, or a group of formula (a) wherein Y is C 1 -C 16 alkyl; and

R ¹ , R ² , R ³ and R ⁴ are the same or different and are independently hydrogen, optionally substituted with 1 to 4 ether-bonded oxygen atoms, C 1 -C 16 alkyl, optionally substituted phenyl, or optionally substituted naphthyl - use for the labeling of hydrocarbons, a hydrocarbon containing the aforementioned leucotrylmethane and a method for detecting leucotrylmethane in the hydrocarbons.

The object of the present invention is to provide new agents for the labeling of hydrocarbons. The requirements for these agents are: they should be readily available and soluble in hydrocarbons, and they should be readily detectable, which means that the compound itself should be visible even in very small amounts, for example by a strong color reaction.

In view of the foregoing, it has been found that the leukotriaryl methanes of the general formula (I), as defined in the introduction, are advantageously used for hydrocarbon labeling.

In all the formulas that appear in this specification,

- 3 alkyl groups can be straight or branched chain.

When a substituted phenyl group or a substituted naphthyl group is present in the formulas herein, the number of substituents in these groups will usually be

1, 2 or 3.

When Z is a substituted phenyl or naphthyl, the substituents include, for example, C 1 -C 16 alkyl, C 1 -C 16 alkoxy, halogen, and amino, C 1 -C 16 monoalkylamino or di (C 1 -C 16 alkyl) amino. group.

3 4

In cases where R, R, R or R are substituted phenyl or substituted naphthyl, the substituent may be, for example, a C 1 -C 16 alkyl group which may have 1-4 ether-bonded oxygen atoms and

C 1 -C 16 alkyl or phenoxy.

When one of the symbols R ¹ , R ² , R ³ and R ⁴ represents a C 1 -C 16 substituted alkyl group, the alkyl group may be substituted, for example, by a hydroxy group, a halogen atom or a cyano group, usually 1, 2 or 3 hydrogen atoms.

2 3 4,

The symbols R, R, R, R and Y may be, for example, methyl, ethyl, propyl, isopropyl, butyl isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, t- pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, , 3,5,5,7-tetramethyl-nonyl, isotridecyl, tetradecyl, pentadecyl or hexadecyl. Of these group names, the isooctyl, isonyl, isodecyl, and isotridecyl group names are so-called trivial names derived from the names of alcohols produced by oxosynthesis [see Ullmann's Encyclopedia of Industrial Chemistry, 5th

Edition, Vol. Al, 290-293. pages 10 and 284 and Vol

285].

In addition, the symbols R ¹ , R ² , R ³ and R ^{4 may} represent, 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, 3,6-dioxa-heptyl, 3,6-dioxa-octyl, 4,8-dioxa-nonyl, 3,7-dioxa-octyl, 3,7-dioxa-nonyl -, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxa-decyl, 4,7-dioxa-undecyl, 3, 6,9-trioxa-decyl, 3,6,9-trioxa-undecyl, 3,6,9-trioxa-dodecyl, 4,7,10-trioxa-undecyl, 3,6,9,12- tetraoxa-tridecyl ·, 3,6,9,12-tetraoxa-tetradecyl, 2-hydroxyethyl, 2-chloroethyl, 2-cyanoethyl, 2- or 3-hydroxypropyl,

2- or 3-chloropropyl, 2- or 3-cyanopropyl, 2- or 4-hydroxybutyl, 2- or 4-chlorobutyl, 2- or 4-cyanobutyl 5-hydroxypentyl, 5-chloropentyl, 5-cyanopentyl, 6-hydroxyhexyl, 5-chlorohexyl or 6-cyanohexyl.

Suitable substituents for the Z symbol include, in addition to the above-mentioned C 1 -C 16 alkyl groups, the following: fluorine, chlorine, and bromine, monomethyl or dimethylamino, monoethyl or diethylamino, monopropyl or dipropyl; amino, monoisopropyl or diisopropylamino, monobutyl or dibutylamino, monopentyl or dipentylamino, monohexyl or dihexylamino, monoheptyl or diheptylamino, monooctyl - or a dioctylamino group, a mono (2-ethylhexyl) amino or a bis (2-ethylhexyl) amino group, a monononyl or dinonylamino group, a monodecyl or didecylamino group , monotridecyl or ditridecylamino, monopentadecyl or dipentadecylamino, monohexadecyl or dihexadecylamino, N-methylethylamino, and methoxy, ethoxy, propoxy, isopropoxy, , butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy i-, 2-methylpentyl-o-benzyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, isooctyloxy, nonyloxy, isonyloxy, decyloxy , isodecyloxy, undecyloxy, dodecyloxy, tridecyloxy, 3,5,5,7-tetramethylnonyloxy, isotridecyloxy, tetradecyloxy, pentadecyloxy or hexadecyloxy.

Preferred for use in the labeling of hydrocarbons are the leucotrylmethane of Formula (I) wherein Z is optionally substituted phenyl.

Further preferred hydrocarbons are the leucotrylmethane of formula (I) wherein R ¹ , R ² , R ³ and R ⁴ are each independently C 1 -C 6 alkyl.

Particular preference is given to the use of the hydrocarbons to denote leucotrylmethane (II) wherein X is hydrogen, amino, C 1 -C 16

A 6-monoalkylamino group or a di (C 1 -C 16 alkyl) amino group, and R ¹ , R ² , R ³ , and R ⁴ are as defined above.

Very particularly preferred hydrocarbons are the leucotrylmethane of formula (II) wherein X is hydrogen or di (C 1 -C 6) alkylamino, in particular dimethylamino, R ¹ , R ² , R ³ and

R is independently C 1-6 alkyl, especially methyl.

The triarylmethane derivatives of formula (I), referred to as leukobases, are either known per se and described in the literature (see, e.g., K. Venkataraman, "The Chemistry of Synthetic Dyes", Vol. II, Academic Press, New York, 1952), or readily obtainable, for example, by the methods outlined in the said monograph. For example, one of the compounds of formula II wherein X is hydrogen,

2 3 z 4

R, R, R and R are methyl, leukomalachite green, and leucocrystalline violet is a triarylmethane derivative of formula (II) wherein X is dimethylamino and R ¹ , R ² , R ³ and R ⁴ is methyl.

In the context of the present invention, it is understood that a leucotrylmethane of formula (I) is added to a hydrocarbon in such a concentration that the color of said hydrocarbon is not at all or only slightly noticeable to the human eye, but the process described below when used, the presence of leucotryrylmethane can be easily visualized, i.e. detected.

A further object of the present invention is to provide hydrocarbons containing one or more leucotrylmethane of formula (I). In these hydrocarbons, the concentration of leucotrylmethane (I) is generally from 1 to 500, preferably from 5 to 50 ppm, and most preferably from about 40 ppm.

Hydrocarbon, as used herein, is understood to mean various aliphatic or aromatic hydrocarbons which are normally liquid. Examples include pentane, hexane, heptane, octane, isooctane, benzene, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, diisopropylnaphthalene, chlorobenzene and dichlorobenzene. Of particular importance in this respect are mineral oil products such as fuels such as petrol, kerosene and diesel, as well as other oils such as fuel oil or motor oils.

Leucotriaryl methanes of formula (I) have been found to be particularly suitable for the identification of petroleum products for which, for some reason, such as taxation, they are readily identifiable. Even if the cost of the label is negligible or low, we need to try to use as little leukobase as possible for the label.

Hydrocarbons may be labeled with the appropriate leucotryrylmethane (I) in pure form or in solution. Solutions include organic solvents such as aromatic hydrocarbons such as toluene, xylene, dodecylbenzene, dnisopropylnaphthalene, and commercially available from Shellsol AB. · ** ·

- ο with a high molecular weight aromatic mixture available under the trade name (Firma Shell). In order to avoid high viscosity, these solutions are generally prepared in a concentration of 20 to 80% by weight of the solution of leucotrylmethane (I) dissolved therein.

Various co-solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol or cyclohexanol to improve solubility; glycols, such as butylethylene glycol or methylpropylene glycol;

amines such as triethylamine, diisooctylamine, dicyclohexylamine, aniline, N-methylaniline, N, N-dimethylaniline, toluidine or xylidine; amino alcohols such as 3- (2-methoxyethoxy) propylamine; cresols, o-cresol, m-cresol or p-cresol;

ketones such as diethyl ketone or cyclohexanone; lactones such as γ-butyrolactone; carbonates such as ethylene carbonate or propylene carbonate; phenols such as tert-butylphenol or nonylphenol; esters such as dimethyl phthalate, diethyl phthalate, bis (2-ethylhexyl) phthalate, ethyl acetate, butyl acetate or cyclohexyl acetate; amides such as N, N-dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone, and mixtures thereof.

It is very easy to trace the labeled hydrocarbon using the leucotriaryl methanes of formula (I) to be used in the present invention, even if, as discussed above, the leukobase used for labeling is present at a concentration of only about 10 ppm or less.

> · · · · · · · · · · · · · · · · · · · · · ··· ·

In some cases, it may also be advantageous to use a mixture of different leucotriaryl methanes of formula (I) to denote the hydrocarbon.

The presence of the leukotrylmethane of formula (I) used in the labeling in the hydrocarbon is preferably detected by treating the labeled hydrocarbon with an oxidizing agent and optionally a protonic acid in the presence of water. As a result of this treatment, a visible color reaction occurs and the leukobase, while producing the corresponding triarylmethane dye, passes into the aqueous phase.

The resulting triarylmethane dye can be represented by the formula (III) wherein Z, R ¹ , R ² , R ³ and R ^{4 have} the meanings given above and ArP is an anion such as sulfate, phosphate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, nitrate, acetate, lactate or citrate ions.

The oxidizing agent may be any conventional inorganic or organic oxidizing agent known per se. Suitable oxidizing agents are, for example, alkali metal permanganates, such as potassium permanganate, alkali metal dichromates, such as sodium and potassium dichromate, and ammonium dichromate, ammonium peroxodisulfate, and alkali metal peroxo, e.g. sodium or potassium peroxo-disulfate, potassium peroxo-monosulfate, iron (III) salts such as iron (III) chloride or ferric (III) sulfate, hydrogen peroxide (in combination with a suitable catalyst) , quinones such as 2,3-dicyano-5,6-dichlorobenzoquinone or 2,3,5,6-tetrachlorobenzoquinone, sodium perborate or

Cerium (IV) salts, such as cerium (IV) sulfate.

Depending on its nature, the oxidizing agent may be used either in the form of an aqueous solution (for example, inorganic oxidizing agents) or in the form of a solution in an organic solvent (usually organic oxidizing agents). Suitable organic solvents for this purpose are, for example, toluene, xylene, cyclohexanone, acetophenone, γ-butyrolactone, (2-ethylhexyl) acetate or esters of phthalic acid.

When organic oxidizing agents are used, the test is carried out in the presence of a dilute aqueous acid such as 5-30% by weight aqueous acetic acid. Of course, an acid such as sulfuric acid may also be present when an inorganic oxidant is used.

The concentration of the oxidant in the solution in aqueous or organic solvent is generally from 0.001 to 5% by weight, preferably 0.01 to 1% by weight of the solution.

When using an aqueous solution of an inorganic oxidant, the amount of acid to be added is very small, for example it can be limited to a single drop.

Generally, larger amounts of acid, such as 5-30% by weight aqueous acetic acid, are used when organic oxidants are used, since the water added with the acid serves as the aqueous phase. In this case, it is recommended that the amount of aqueous acid be approximately equal to the amount of hydrocarbon sample to be tested.

Usually, the appropriate procedure is followed if the invention

Approximately 1-5 ml of the labeled hydrocarbon is taken from -11rine and then at a temperature of 10-100 ° C, preferably 20-80 ° C, from 2-10 ml of a solution of an organic oxidant in an organic solvent, and 1-5 ml. or about 1 to 5 ml of an aqueous solution of an inorganic oxidant, if appropriate in the presence of an acid. Preferably, the treatment is performed as if the hydrocarbon phase was extracted with the aqueous phase, i.e., the biphasic mixture was shaken well.

For use in the present invention, it is desirable to select triarylmethane leuco compounds which are readily available and highly soluble in hydrocarbons, and are readily detectable because, due to the vigorous color reaction, even very small amounts of the label material are visible.

In the following section, examples are provided to further illustrate the invention.

Example 1:

of xylene solution containing 10 ppm of leucocrystalline violet and 3.5 ml of a solution of 2,3-dicyano-5,6-dichlorobenzoquinone (50 ppm) also in xylene and after 1 minute shake with 2 ml of 20% acetic acid. the mixture. Shaking is continued until the total amount of dye is dissolved in the aqueous phase and the aqueous phase shows an intense purple color.

-122. example:

of xylene solution containing 10 ppm leukomalachitic green and 3.5 ml of 50 ppm solution of 2,3-dicyano-5,6-dichlorobenzoquinone in xylene.

After 1 minute, the mixture is shaken with 2 ml of 20% w / w acetic acid and shaking until the dye is completely dissolved in the aqueous phase. The aqueous phase then shows an intense green color.

Example 3:

A solution containing 10 ppm of leucocrystalline violet was prepared with commercially available diesel oil, and a 2 ml sample of the solution was mixed with 3.5 ml of 0.05% w / w solution of 2,3-dicyano-5,6-dichlorobenzoquinone in xylene. After 1 minute, the mixture is shaken with 2 ml of 20% (w / w) acetic acid, and shaking is continued until all the dye is dissolved in the aqueous phase. At this time, the aqueous phase shows an intense purple color.

Example 4:

A commercial solution of 10 ppm leukomalachite green solution is prepared with commercial diesel oil, a 2 ml sample is taken from this solution and 3.5 ml of 0.05% w / w 2,3-dicyano-5,6-dichlorobenzoquinone in xylene is prepared. -oldattal. After 1 minute, shake the mixture with 2 ml of 20% w / w acetic acid and shake until the dye is completely dissolved in the aqueous wood.

-13zisba. The aqueous phase then shows an intense green color.

Example 5:

Shake with 0.1 ml of a 0.1 wt% leucocrystalline violet solution in toluene with 1.5 ml of a 0.1 wt% ferric chloride solution, and after 15 seconds the mixture was heated to 70 ° C. It is well observed that the aqueous phase turns violet blue.

Example 6:

A 0.1% (w / w) solution of leucocrystalline violet in toluene (1.5 ml) was shaken with 0.1% (w / w) aqueous sodium peroxo-monosulfate for 15 seconds and the mixture was heated to 70 ° C. It is well observed that the aqueous phase turns violet blue.

Example 7:

To 0.1 ml of a 0.1 wt% leucocrystalline violet solution in toluene, 1.5 ml of a 0.1 wt% aqueous potassium permanganate solution and 2 drops of 10 wt% sulfuric acid are added. The mixture is shaken for 15 seconds while the potassium permanganate color disappears and the aqueous phase visibly turns violet blue.

Example 8:

To 0.1 ml of a 0.1 wt% leucocrystalline violet solution in toluene is added 1.5 ml of a 0.1 wt% aqueous solution of potassium permanent 14ganate and 2 drops of 10 wt% sulfuric acid. After shaking for 15 minutes, the mixture was heated to 70 ° C, whereupon a violet blue color appeared in the aqueous phase.

Claims (6)

Claims 1. A leucotrylmethane of formula (I): wherein Z is optionally substituted phenyl, optionally substituted naphthyl, or a group of formula (a) wherein Y is C 1 -C 16 alkyl; and 12 3x4 x R, R, R and R are the same or different and each independently represents a hydrogen atom, an optionally substituted and unsubstituted C1-C16 alkyl group optionally substituted with 1 to 4 ether oxygen atoms, an optionally substituted phenyl group or an optionally substituted naphthyl group. . Use of leucotiaryl methanes according to claim 1, characterized in that Z is an optionally substituted phenyl group. Use of leucotiaryl methanes according to claim 1, characterized in that R ¹ , R ² , R ³ and R ⁴ are each independently C 1 -C 16 alkyl. 4. The use of leucotiarylmethane according to claim 1, wherein the leucotiarylmethane is a compound of formula II wherein X is hydrogen, amino, C 1 -C 16 monoalkylamino or di (C 1 -C 16 alkyl) amino; and R ¹ , R ² , R ³ and R ⁴ are as defined in claim 1. -16 • · · · · · · · · ······· · · ··· A hydrocarbon containing as marker an one or more leukotrylmethane of formula (I) according to claim 1. 6. A method for detecting the presence of the leucotrylmethane of formula I in claim 1 in a hydrocarbon, wherein said hydrocarbon is treated with an oxidizing agent in the presence of water and optionally a protonic acid.