EP0714429A1

EP0714429A1 - Use of aminotriarylmethanes for marking hydrocarbons, and new aminotriarylmethanes

Info

Publication number: EP0714429A1
Application number: EP94918872A
Authority: EP
Inventors: Ulrike Schloesser; Karin Heidrun Beck
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1993-06-21
Filing date: 1994-06-15
Publication date: 1996-06-05
Also published as: JPH08511551A; DE4320456A1; NO955201L; WO1995000606A1; US5990327A; CA2162252A1; NO955201D0

Abstract

The invention concerns the use, for making hydrocarbons, of aminotriarylmethanes of formula (I) in which the ring A may be benzoanellated; R?1 and R2¿ are optionally substituted C¿1?-C13 alkyl or optionally substituted phenyl or R?1 and R2¿ together with the nitrogen atom to which they are bound are a heterocyclic group, whereby R1 may also be hydrogen; R?3 and R4¿ are optionally substituted C¿1?-C20 alkyl, whereby R?3¿ may be hydrogen; and X?1 and X2¿ are optionally substituted C¿1?-C13 alkyl, a group of the formula NR?1R2¿ or one of the groups X?1 and X2¿ or hydrogen. The invention also concerns hydrocarbons containing such aminotriarylmethanes, a method of detecting the presence of such aminotriarylmethanes in hydrocarbons and new aminotriarylmethanes.

Description

Use of aminotriarylmethanes for labeling hydrocarbons and new aminotriarylmethanes

description

The present invention relates to the use of aminotryl methanes of the formula I.

in which the ring A can be fused to benzo and

R ¹ and R ^{2 are the} same or different and, independently of one another, each Cχ-Ci ₃ alkyl, which can be interrupted by 1 to 3 oxygen atoms in ether function and is optionally substituted by amino or hydroxy, optionally substituted Phenyl or R ¹ and R ² together with the nitrogen atom connecting them a 5- or 6-membered saturated heterocyclic radical, which may have a further hetero atom, or R ¹ also hydrogen,

R ³ and R ⁴ are identical or different and independently of each voneinan¬ _{Cι-C2o-alkyl} tome by 1 to 4 Sauerstoffa¬ may be interrupted in ether function and, where appropriate, by amino, hydroxy or phenyl, or R ³ also hydrogen and

X ¹ and X ^{2 are the} same or different and, independently of one another, each -C 1 -C ₃ -alkyl, which can be interrupted by 1 to 3 oxygen atoms in ether function and is optionally substituted by amino or hydroxyl, a radical of the formula NR ^X R ² , wherein R ¹ and R ² each have the above have meaning, or one of the two radicals X ¹ and X ² also denote hydrogen,

for marking hydrocarbons, hydrocarbons containing the aminotriarylmethanes of the formula I, a method for the detection of the aminotriarylmethanes of the formula I in hydrocarbons and new aminotriarylmethanes.

The use of triarylmethane dyes or triarylmethane carbinols for marking mineral oils is known from US Pat. No. 5,145,573.

The object of the present invention was to provide new marking agents for hydrocarbons. The new marking agents should be easily accessible and readily soluble in hydrocarbons. In addition, they should be easy to prove. Even very small amounts of markers should be made visible by a strong color reaction.

Accordingly, it has been found that the aminotriarylmethanes of the formula I described at the outset are advantageously suitable for labeling hydrocarbons.

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

If substituted alkyl groups occur in the above formula I, they generally have 1 or 2 substituents.

When substituted phenyl groups occur in the above formula I, e.g. Ci-C-j-alkyl or -C-alkoxy come into consideration. The phenyl groups generally have 1 to 3 substituents.

If R ¹ and R ² together with the nitrogen atom connecting them represent a 5- or 6-membered saturated heterocyclic radical, which may have a further heteroatom, for example pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl or N- (Cχ-C Alkyl) piperazinyl come into consideration.

R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl,

Undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl (the above terms isooctyl, isononyl, isodecyl and iso- tridecyl are trivial names and come from the alcohols obtained after oxo synthesis - cf. see also Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436), 2-hydrσxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, 5-hydroxypentyl , 6-hydroxyhexyl, 5-hydroxy-3-oxapentyl, 2-aminoethyl, 2- or 3-aminopropyl, 2- or 4-aminobutyl, 5-aminopentyl, 6-aminohexyl, 7-aminoheptyl, 8-aminooctyl, 5 -Amino-3-oxapentyl, 6-amino-3-oxahexyl, 6-amino-4-oxahexyl, 7-amino-4-oxaheptyl, 8-amino-3, 6-dioxaoctyl, 3-aminoprop-2-yl, 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-dioxaheptyl, 3, 6-dioxoxyctyl, 4, 8-dioxanonyl, 3,7-dioxaoctyl, 3, 7-dioxanonyl, 4,7-dioxaxoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4, 8-dioxadecyl, 3, 6, 9-trioxadecyl or 3, 6, 9-trioxaundecyl.

R ³ and R ⁴ are furthermore, for example, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, benzyl, 1- or 2-phenylethyl, 3, 6, 9-trioxadodecyl, 3, 6, 9,12- Tetraoxatridecyl or 3,6,9,12-tetraoxatetradecyl.

Aminotriarylmethanes of the formula I in which R ¹ and R ² independently of one another are each -C ¹ -C 4 -alkyl or optionally substituted phenyl or R ^{1 are} also hydrogen are preferably used for labeling hydrocarbons.

Also preferred are aminotriarylmethanes of the formula I in which R ³ and R ⁴ independently of one another are each C ₆ -C ₃ alkyl, in particular C ₆ -C ₃ alkyl, which can be interrupted by 1 or 2 oxygen atoms in ether function , or R ³ also mean hydrogen, used for marking hydrocarbons.

Also preferred are aminotriarylmethanes of the formula I in which X ¹ and X ² independently of one another are each C ¹ -C ₄ -alkyl, C 1 -C ₄ -dialkylamino or one of the two radicals X ¹ and X ² also mean hydrogen for marking hydrocarbons used.

The present invention further provides hydrocarbons containing one or more of the aminotriaryl methanes of the formula I. Preference is given to hydrocarbons containing one or more of the aminotriarylmethanes of the formula I in which R ¹ and R ² independently of one another are each C ¹ -C ₄ -alkyl or optionally substituted phenyl or R ^{1 are} also hydrogen.

Also preferred are hydrocarbons containing one or more of the aminotriarylmethanes of the formula I in which R ³ and R ⁴ are each independently C ₆ -C ₃ alkyl, which can be interrupted by 1 or 2 oxygen atoms in ether function, or R ^{3 is} also hydrogen mean.

Also preferred are hydrocarbons containing one or more of the aminotriarylmethanes of the formula I in which X ¹ and X ² independently of one another are each C ¹ -C ₄ -alkyl, C 1 -C ₄ dialkylamino or one of the two radicals X ¹ and X ² and also hydrogen mean.

Hydrocarbons in the sense of the invention are understood to mean aliphatic or aromatic hydrocarbons which are present in the 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 engine oil.

The aminotriarylmethanes of formula I are particularly suitable for marking mineral oils for which marking is required, e.g. for tax reasons. In order to keep the costs of the marking low, the aim is to use the smallest possible amount of marking agent for the marking.

To mark hydrocarbons, the aminotriaryl methanes of the formula I are used either in bulk or in the form of solutions. Organic solvents are suitable as solvents. Aromatic hydrocarbons, such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatics, which is commercially available under the name Shellsol® AB (Shell), are preferably used. In order to avoid a high viscosity of the resulting solutions, a concentration of aminotriarylmethane I of 20 to 80% by weight, based on the solution, is generally chosen.

Using the aminotriarylmethanes of the formula I to be used according to the invention, it is very easy to detect marked hydrocarbons, even if the marking agents are only present in a concentration of approximately 10 ppm or less. The detection of the aminotriaryl methanes of the formula I used as marking agents in hydrocarbons is advantageously achieved if the mineral oil is treated with an aqueous alcoholic medium which contains a protonic acid and optionally a halide of the metals zinc, aluminum or tin.

When the protonic acid and optionally the metal halide are added to the marked hydrocarbon, a clearly visible color reaction results, with the formation of a triarylmethane dye, which passes into the aqueous-alcoholic phase.

Suitable alcohols are e.g. Ethanol, propanol or 1-methoxypropan-2-ol. The use of ethanol is preferred.

Suitable protonic acids for the process according to the invention are in particular so-called strong acids, i.e. Protonic acids whose pKa is <3.5. Examples of such acids are inorganic or organic acids, such as perchloric acid, hydroiodic acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, benzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, oxalic acid, maleic acid, chloroacetic acid, dichloroacetic acid, dichloroacetic acid or bromoacetic acid. In some cases it may be advantageous to use these acids e.g. by adding acetic acid.

Particularly noteworthy are inorganic acids, with hydrochloric acid or sulfuric acid being of particular importance.

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

Zinc chloride is particularly noteworthy.

It is usually sufficient to shake an amount of approximately 20 ml of the mineral oil labeled according to the invention with 10 ml of an aqueous alcoholic solution of a protonic acid, optionally with the addition of the metal halide, in order to obtain this color reaction. It is also possible to use an aqueous-alcoholic solution of the metal halide alone, since this also reacts acidic.

The concentration of the protonic acid in the aqueous-alcoholic solution is generally 5 to 50% by weight, preferably 10 to 30% by weight. The concentration of metal halide is generally generally at 10 to 20 wt .-% and those of alcohol in general at 10 to 40 wt .-%.

Preferred is a method for the detection of aminotriarylmethanes of the formula 1, -R ¹ and R ² independently of one another in each case C ¹ -C ₄ -alkyl or optionally substituted phenyl or R ^{1 is} also hydrogen.

Also preferred is a method for the detection of amino-triarylmethanes of the formula I in which R ³ and R ⁴ independently of one another are each C ₆ -C ₃ alkyl, which can be interrupted by 1 or 2 oxygen atoms in ether function, or R ³ also mean hydrogen.

Also preferred is a method for the detection of amino triarylmethanes of the formula I in which X ¹ and X ² independently of one another are each C 1 -C ₄ -alkyl, C 1 -C ₄ dialkylamino or one of the two radicals X ¹ and X ² also mean hydrogen.

The present invention further provides amino triaryl methanes of the formula Ia

N.

Rl ^ ^" R ²

in which the ring A can be fused to benzo and

R ¹ and R ^{2 are} identical or different and, independently of one another, are each C 1 -C ₃ -alkyl which can be interrupted by 1 to 3 oxygen atoms in ether function and is optionally substituted by amino or hydroxyl, optionally substituted Phenyl or R ¹ and R ² together with the nitrogen atom connecting them a 5- or 6-membered saturated heterocyclic radical, the one may have further heteroatoms, or R ^{1 may} also be hydrogen,

Y ¹ and Y ² are identical or different and independently of each Cι ~ C ₂ o alkyl which tome by 1 to 4 Sauerstoffa¬ from each other is interrupted in ether function and is optionally substituted by amino, hydroxy or phenyl, or R ³ also Hydrogen and

X ¹ and X ^{2 are the} same or different and, independently of one another, are each C 1 -C ₃ -alkyl, which can be interrupted by 1 to 3 oxygen atoms in ether function and optionally substituted by amino or hydroxyl, a radical of the formula NR ¹ R ² , in which R ¹ and R ² each have the meaning given above, or one of the two radicals X ¹ and X ² also denotes hydrogen.

With regard to the exemplary listing of the individual residues in formula Ia, reference is made to the statements made above.

Aminotriarylmethanes of the formula Ia are preferred, in which R ¹ and R ² independently of one another are each C 1 -C 4 -alkyl or optionally substituted phenyl or R ^{1 is} also hydrogen.

Also preferred are aminotriarylmethanes of the formula Ia in which Y ¹ and Y ² independently of one another are each C ₆ -C ₃ alkyl which is interrupted by 1 or 2 oxygen atoms in ether function, or R ^{3 is} also hydrogen.

Also preferred are aminotriarylmethanes of the formula Ia in which X ¹ and X ² independently of one another are each C 1 -C 4 -alkyl, C 1 -C 4 -dialkylamino or one of the two radicals X ¹ and X ^{2 are} also hydrogen.

The new aminotriarylmethanes of the formula Ia, like the other aminotriarylmethanes of the formula I, which are known from EP-A-433 813, can be prepared by methods known per se, such as those mentioned in EP-A-433 813, be preserved. For example, a triarylmethane base of the formula II

in which R ¹ , R ² , X ¹ , X ² and the ring A each have the abovementioned meaning, with an amine of the formula purple or Illb

R ³ Y ^l

NH (purple) NH (Illb)

R ⁴ Y ²

where R ³ , R ⁴ , Y ¹ and Y ² each have the abovementioned meaning, implement.

The new aminotriarylmethanes of the formula Ia have good solubility in organic solvents and, as already stated above, are advantageously suitable for labeling hydrocarbons.

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

example 1

A) Manufacturing

14.2 g of ethyl violet base of the formula

and 4 g of 3- (2-ethylhexyloxy) propylamine were refluxed in 100 ml of toluene for 7 hours. After cooling, the reaction mixture was washed with water and dried over sodium sulfate. After stripping off the solvent, 16.9 g of a compound of the formula were obtained

NH-C ₃ H ₆ OCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉

N (C ₂ H ₅ ) ₂ [λmax (in acetic acid): 587 nm]

which still contained about 10% of starting material as a by-product.

The aminotriarylmethanes of the formula listed in the following table are obtained in an analogous manner

NL ⁴

L ³

receive.

B) application

General rule

Commercially available diesel fuel is mixed with a 40% by weight solution of the marking agent in a commercially available mixture of higher flavors - Shellsol ^® AB (Shell).

The addition of the marking agent is 10 ppm.

20 ml of marked diesel fuel are adjusted to 2 with 20 ml of reagent solution (10% by weight zinc chloride solution in a water / ethanol mixture (60:40 v / v), pH value by adding 85% by weight acetic acid) shaken vigorously. The lower, aqueous phase is clearly recognizable. The aqueous phase can be measured photometrically against a solution of known concentration.

Good results were achieved in each case with the marking substances listed above (Examples 1 to 12).

Claims

claims

1. Use of aminotriarylmethanes of the formula I.

R ³ R ⁴ N

in which the ring A can be fused to benzo and

R ¹ and R ^{2 are the} same or different and, independently of one another, are each C 1 -C ₃ -alkyl which can be interrupted by 1 to 3 oxygen atoms in ether function and is optionally substituted by amino or hydroxyl, optionally substituted phenyl or

R ¹ and R ² together with the nitrogen atom connecting them represent a 5- or 6-membered saturated heterocyclic radical which may have a further hetero atom, or R ¹ also hydrogen,

R ³ and R ⁴ are identical or different and independently of one another, each _{Cι-C2o-alkyl} erstoffatome by 1 to 4 Sau¬ may be interrupted in ether function and optionally substituted by amino, hydroxy or phenyl, or R ³ also hydrogen and

X ¹ and X ^{2 are the} same or different and, independently of one another, are each C 1 -C ₃ -alkyl, which can be interrupted by 1 to 3 oxygen atoms in ether function and optionally substituted by amino or hydroxy, a radical of the formula NR ⁱ R ² , in which R ¹ and R ² each have the abovementioned meaning, or one of the two radicals X ¹ and X ² also mean hydrogen,

for marking hydrocarbons.

2. Use of aminotriarylmethanes according to claim 1, characterized in that R ¹ and R ² independently of one another are each C ¹ -C ₄ -alkyl or optionally substituted phenyl or R ^{1 is} also hydrogen.

3. Use of aminotriarylmethanes according to claim 1, characterized in that R ³ and R ⁴ independently of one another each C6-Ci ₃ alkyl, which can be interrupted by 1 or 2 oxygen atoms in ether function, or R ³ also mean hydrogen .

4. Use of aminotriarylmethanes according to Claim 1, characterized in that X ¹ and X ² independently of one another are each C ¹ -C ₄ -alkyl, C 1 -C ₄ -dialkylamino or one of the two radicals X ¹ and X ^{2 are} also hydrogen.

5. hydrocarbons containing one or more Aminotria¬ rylmethane of formula I according to claim 1.

6. Method for the detection of the presence of aminotriarylmethane of formula I.

in which the ring A can be fused to benzo and

R ¹ and R ^{2 are} identical or different and, independently of one another, are each C 1 -C ₃ -alkyl, which can be interrupted by 1 to 3 oxygen atoms in ether function and is optionally substituted by amino or hydroxy, optionally substituted phenyl or R ¹ and R ² together with the nitrogen atom connecting them form a 5- or 6-membered saturated terocyclic radical, which may have a further heteroatom, or R ¹ also hydrogen,

R ³ and R ⁴ are identical or different and independently of one another each _{Cι-C2o-alkyl} erstoffatome by 1 to 4 Sau¬ may be interrupted in ether function and optionally substituted by amino, hydroxy or phenyl, or R ³ also hydrogen and

X ¹ and X ^{2 are} identical or different and, independently of one another, are each C 1 -C ₃ -alkyl, which can be interrupted by 1 to 3 oxygen atoms in ether function and optionally substituted by amino or hydroxy, a radical of the formula NR ¹ R ² , in which R ¹ and R ² each have the abovementioned meaning, or one of the two radicals X ¹ and X ² also mean hydrogen,

in hydrocarbons, characterized in that the hydrocarbon is treated with an aqueous alcoholic medium which contains a protonic acid and optionally a halide of the metals zinc, aluminum or tin.

Aminotriarylmethanes of the formula la

in which the ring A can be fused to benzo and

R ¹ and R ^{2 are} identical or different and, independently of one another, are each C 1 -C ₃ -alkyl which can be interrupted by 1 to 3 oxygen atoms in ether function and is optionally substituted by amino or hydroxy, optionally substituted phenyl or R ¹ and R ² together with the embroidery a 5- or 6-membered saturated heterocyclic radical which may have a further heteroatom, or R ^{1 is} also hydrogen,

Y ¹ and Y ^{2 are} identical or different and, independently of one another, each _{Cι-C2o-alkyl} erstoffatome by 1 to 4 Sau¬ is suspended in ether function and is optionally sub¬ stituiert by amino, hydroxy or phenyl, or R ³ also hydrogen and

X ¹ and X ^{2 are} identical or different and, independently of one another, are each C 1 -C ₃ -alkyl, which can be interrupted by 1 to 3 oxygen atoms in ether function and is optionally substituted by amino or hydroxyl, a radical of the formula NR ¹ R ² , wherein R ¹ and

R ² each have the abovementioned meaning, or one of the two radicals X ¹ and X ² also mean hydrogen.