CA2193887A1 - Use of leucotriarylmethanes for marking hydrocarbons - Google Patents
Use of leucotriarylmethanes for marking hydrocarbonsInfo
- Publication number
- CA2193887A1 CA2193887A1 CA002193887A CA2193887A CA2193887A1 CA 2193887 A1 CA2193887 A1 CA 2193887A1 CA 002193887 A CA002193887 A CA 002193887A CA 2193887 A CA2193887 A CA 2193887A CA 2193887 A1 CA2193887 A1 CA 2193887A1
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- leuco
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/003—Marking, e.g. coloration by addition of pigments
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/007—Coloured or dyes-containing lubricant compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
- C10M2215/226—Morpholines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/30—Heterocyclic compounds
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention concerns the use, as markers for hydrocarbons, of leucotriarylmethanes of formula (I) in which Z is an aromatic carbocyclic or heterocyclic group and R1, R2, R3 and R4 are hydrogen, optionally substituted C1-C16 alkyl, optionally substituted phenyl or optionally substituted naphthyl. The invention also concerns hydrocarbons containing such leucotriarylmethanes and a method of detecting leucotriarylmethanes in hydrocarbons.
Description
BASF Alctienges~ ft 930541 O.Z 0050/44978 U~e o~ leuco triarylmethanes for marking hydrocarbons ~he preæent invention relates to the use of leuco triarylmethanes 5 of the formula I
Rl I
--CEI/¢~N~ R2 (I), ~ N~
where 20 z i8 substituted or unsubstituted phenyl, substituted or unsub-stituted naphthyl or a radical of the formula ~ , where y Y is Cl--Cl~alkyl, and 30 Rl, R2, R3 and R4 are identical or different and each i8 indepen-dently of the others hydrogen, Cl--Cl6--alkyl with or without interrupt~on by f rom 1 to 4 oxygen atoms in ether f unction and with or without substitution, substituted or unsubsti-tuted phenyl or substituted or unsubstituted naphthyl, as markers for hydrocarbons, to hydrocarbons comprising the abovementioned leuco triarylmethanes, and to a method f or detec-ting leuco triarylmethanes in hydrocarbons.
40 It is an object of the present invention to provide ~ovel markers for hydrocarbons. ~he novel markers should be readily obtainable and soluble in hydrocarbons. They should also be simple to detect; spPr;f;--~11y~ even very small amounts of markers should be v;c;h11i7~hl~ through a strong color reaction.
BASF Aktieng~c~llcrh~ft 930541 O.Z. 0050/44978 a We have found that this object is achieved by the above-defined leuco triarylmethanes of the formula I.
Any alkyl appearing in the formulae mentioned herein may be 5 straight-chain or branched.
In any 6ubstituted phenyl or naphthyl appearing in the formulae mentioned herein the number of ~ubstituents is generally from 1 to 3.
Substituted phenyl or naphthyl Z may have as substituents for example C1~16--alkyl, C1--C1~alkoxy, halogen, amino or mono--or di ( Cl--C16--alkyl ) amino .
15 Any substituted phenyl or naphthyl R1, R2, R3 or R4 may have as substituents for example C1--C16--alkyl with or without interruption by from 1 to 4 oxygen atoms in ether function, Cl--C16--alkoxy or phenoxy .
20 Substituted C1--C16--alkyl R1, R2, R3 or R4 may have as substituents for example hydroxyl, halogen or cyano. The number of sub-stituents is generally 1 or 2.
R1, R2, R3, R4 and Y are each for example methyl, ethyl, propyl, 25 isopropyl, butyl, isobutyl, sec--butyl, pentyl, isopentyl, neo-pentyl, tert--pentyl, hexyl, 2--methylpentyl, heptyl, octyl, 2~thylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3, 5, 5, 7--tetramethylnonyl, i5 otri-decyl, tetradecyl, pentadecyl or hexadecyl ~ the above designa-30 tions isooctyl, isononyl, 1sodecyl and isotridecyl are trivialnames derived from the oxo process alcohols -- cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edltion, Vol. A1, pages 290 to 293, and Vol. A lO, pages 284 and 285).
35 R1, R2, R3 and R4 may each also be ~or example 2~ethoxyethyl, 2~thoxyethyl, 2--propoxyethyl, 2--is LI~LU~O~LY :thyl, 2--butoxyethyl, 2-- or 3--methc,.~y~L-,~yl, 2-- or 3~thoxypropyl, 2-- or 3--propoxy-propyl, 2-- or 3--butoxypropyl, 2-- or 4--methoxybutyl, 2-- or 4~thoxybutyl, 2--or 4--~L~ YbU~Y1~ 3,6~ioxaheptyl, 3,6--dioxy-40 octyl, 4, 8--dioxanonyl, 3, 7--dioxaoctyl, 3, 7~ioxanonyl, 4, 7--dioxa-octyl, 4,7--dioxanonyl, 2--or 4--butoxybutyl, 4,8--dioxadecyl, 4~ 7~?~ n~ n~ . yl~ 3, 6, 9--trioxadecyl, 3, 6, 9--tr~ r yl, 3,6,9--tri~Y~t3n~l~cyl, 4,7,10--tr~nY~Iln~1~cyl~ 3,6,9,12--LeLLc~v~LLi--decyl, 3, 6, 9, 12--tetraoxatetradecyl, 2--hydL~--y~Lhyl, 2--chloro-45 ethyl, 2--cyanoethyl, 2--or 3--IIYdL~ Y~ Y1~ 2--or 3--chloropropyl,2-- or 3--cyanopropyl, 2--or 4--lly ILo~ybuLyl~ 2-- or 4--chlorobutyl, _ _ . . . .. .. . _ . _ .. . ... . .. _ _ . _ . . . .
BASF Aktiengese~ rha~t 930541 O.Z. 0050/44978 3 2~ 93887 2-- or 4--cyanobutyl, 5--hydroxypentyl, 5--chloropentyl, 5~yano-pentyl, 6--hydroxyhexyl, 5--chlorohexyl or 6--cyanoheYyl.
Suitable substituents for Z, as well as the aforementioned 5 C1--C16--alkyl radicals, include for example fluorine, chlorine, bromine, mono-- or dimethylamino, mono-- or diethylamino, mono-- or dipropylamino, mono-- or diisopropylamino, mono-- or dibutylamino, mono--or dipentylamino, mono-- or dihexylamino, mono-- or diheptyl-amino, mono--or dioctylamino, mono-- or bis(2--ethylhexyl~amino, 10 mono--or dinonylamino, mono--or didecylamino, mono-- or diundecyl-amino, mono-- or didodecylamino, mono-- or ditridecylamino, mono--or ditetradecylamino, mono- or dipentadecylamino, mono-- or ~1~ hpy~A~r-ylamino~ N--methyl-N--ethylamino, methoxy, ethoxy, propoxy, is~ p-~Ay~ butoxy, isobutoxy, sec--butoxy, pentyloxy, 15 isopentyloxy, neopentyloxy, tert--pentyloxy, hexyloxy, 2--methyl-pentyloxy, heptyloxy, octyloxy, 2--ethylhexyloxy, isooctyloxy, nonyloxy, isononyloxy, decyloxy, isodecyloxy, undecyloxy, dodecyloxy, tridecyloxy, 3,5,5,7--tetramethylnonyloxy, isotri-decyloxy, tetradecyloxy, pentadecyloxy or hexadecyloxy.
Preference for marking hydrocarbons is given to the use of leuco triarylmethanes of the formula I where Z i~3 substituted or unsub-~tituted phenyl.
25 Preference for marking hydrocarbons is further given to the use of leuco triarylmethanes of the formula I where R1, R2, R3 and R~
are each i nrl~rp~s~ntly of the others Cl--C6--alkyl .
Particular preference for the marking of hydrocarbons is given to 30 the use of leuco triarylmethanes of the formula II
Rl ~ CE~ N~ R2 [~ (II), R3~ ~ R4 where X is hydrogen, amino or mono-- or di(C1--C16--alkyl)amino and R1, R2, R3 and R~ are each as defined above.
45 Very particular preference for the marking of hydrocarbons is given to the use of leuco triarylmethanes of the formula II where X is hydrogen or di(Cl--C6--alkyl)amino, PCp~ y dimethylamino, _ _ _ , . , ,, . ,, , , _ _ ,, _ ,,,, , ,,, _ _ _ _ _ _ _ BASF ~l~ti-~n~c~llcchaft 930541 O.Z. 0050/44978 and Rl, R2, R3 and R4 are each ;n~lQr~n~Qrltly of the others Cl~alkyl, especially methyl.
The leuco triarylmethanes of the formula I are known per se and 5 ~IQ~rr~hed for example in 1~. Venkataraman, The Chemistry of Synthetic Dyes, Vol. II, Academic Press, New York, 1952, or can be obtained for example by the methods mentioned therein.
The leuco triarylmethane of the formula II where X is hydrogen 10 and R1, R2, R3 and R4 are each methyl is leuco malachite green, while the leuco triarylmethane of the formula II where X is dimethylamino and Rl, R2, R3 and R4 are each again methyl is leuco crystal violet.
15 Marking for the purposes of the present invention is the addition to hydrocarbons of the leuco triarylmethanes of the formula I in such a concentration that, to the human eye, the hydrocarbons have barely any or no visible color, but the leuco triaryl-methanes o~ the formula I are readily and distinctly visibly 20 detectable by the methods of detection more particularly described herein.
The present invention further provides hydrocarbons containing one or more o~ the leuco triarylmethanes of the formula I. The 25 cvl.cel,~Lation of the leuco triarylmethanes of the formula I in the hydrocarbons is generally from 1 to 500 ppm, preferably from 5 to 50 ppm, especially about 40 ppm.
Hydrocarbons for the purposes of the present invention are 30 aliphatic or aromatic hydrocarbons which are liquid under standard conditions, for example pentane, hexa~le, heptane, octane, isooctane, benzene, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, diisopropylnaphthalene, chlorobenzene or dichlorobenzene. More particularly, they are 35 mineral oils, for example motor fuels, such as gasoline, kerosine or diesel fuel, or oils, such as heating oil or engine oil.
The leuco triarylmethanes of the formula I are especially suitable for marking mineral oils where some form of marking is 40 mandatory, for example for tax reasons. To keep the costs for this to a minimum, it is desirable to keep the amount of marker used to a minimum.
To mark hydrocarbons, the leuco triarylmethanes of the formula I
45 are used either without a solvent or in the form of solutions.
Suitable solvents are organic solvents. Preference is given to using aromatic hydrocarbons, such as toluene, xylene, , . ... _ .. _ .. ... .. , , , _ _ _ _ BASF ~l~ti ,~llschaft 930541 O.Z. 0050/44978 dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatlcs available from Shell as Shellsol(~) A3. To avoid the re-sulting solution having a high viscosity, the concentration of leuco triarylmethane I chosen for the solution generally ranges 5 from 20 to 80% by weight, based on the solution.
The solubility may be improved by using ~urther, co-solvents, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, 10 octanol, 2--ethylhexanol or cyclohexanol, glycols, such as butyl-ethylene glycol or methylpropylene glycol, amines, such as triethylamine, diisooctylamine, dicyclohexylamine, aniline, N--methylaniline, N,N--dimethylaniline, toluidine or xylidine, AlkAn~r~in~ such as 3--(2--methoxyethoxy)propylamine, o-cresol, 15 m--cresol or p-cresol, ketones, such as diethyl ketone or cyclo-hexanone, lactones, such as y--butyrolactone, carbonates, such as ethylene carbonate or propylene carbonate, phenols, such as t--butylphenol or nonylphenol, esters, such as methyl phthalate, ethyl phthalate, 2--ethylhexyl phthalate, ethyl acetate, butyl 20 acetate or cyclohexyl acetate, amides, such as N,N--dimethyl-formamide, N,N--diethylacetamide or N--methylpyrrolidone, or mixtures thereof.
The leuco triarylmethanes of the formula I to be used according 25 to the present invention permit very simple detection of marked hydrocarbons, even if, as mentioned above, the marker substances are present only in a concentration o~ about 10 ppm or less.
In some ca3es it is also advantageous for the marker to be used 30 to comprise mixtures between leuco triarylmethanes of the formula I.
The presence in hydrocarbons of the leuco triarylmethanes of the formula I used as markers is advantageously detected on treating 35 the marked hydrocarbon with an oY; ~ ; n~ agent and optlonally a protic acid in the presence of water.
This treatment gives rise to a clearly visible color rRaction and the leuco triarylmethane I forms a triarylmethane dye and trans-40 fers to the aqueous phase.
The resulting triarylmethane dye conforms to the formula III
BA'SF Aktieng~c~llc~-hAft 930541 O.Z. 0050/44978 1 6 21 93&87 C~N~ R2 ~n~
1 (III), ~ N~ 4 where Z, Rl, R2, R3 and R4 are each as defined above and An~ is the equivalent of an anion (eg. sulfate, hydrogensulfate, phos-phate, hydL~,g~llphc,~hate, di~lyd~gt~ hosphate~ nitrate, acetate, 15 lactate or citrate).
Suitable ~Y; ~; 7; nq agents include for example customary, inorganic or organic ~Y;ri;7;ns agents known per se, such as alkali metal r~r~~n~n~tes~ eg. potassium permanganate, ammonium 20 dichromate, alkali metal dichromates, eg. sodium or potassium dichromate, ; peroxodisulfate, alkali metal peroxo-disulfates such as sodium or potassium peroxodisulfate, potas3ium pe~ sulfate, iron(III) salts, eg. iron(III) chloride or iron(III) sulfate, hydrogen peroxide (in combination with 25 suitable catalysts ), quinones, eg . 2, 3--dichloro-5, 6--dicyanobenzo-quinone or 2, 3, 5, 6--tetrachlorobenzoquinone, sodium perborate or cerium(IV) salts, eg. cerium(IV) sulfate.
~oronlling on the nature of the nYi~7;n~ agents, they can be used 30 either in the form of an aqueous solution (inorganic ~Y;~;7;
agents) or in the form of a solution in an organic solvent (organic ~Y;~;7;n~ agents~. Suitable organic solvents include for example toluene, xylene, cy~r,hFY~n~n~, acet~honnn~, y--butyro-lactone, 2--ethylhexyl acetate or esters of phthalic acid.
If organic ~Y;~l;7;nq agent~ are used, a dilute aqueous acid is employed, for example from 5 to 30~ strength by weight aqueoua acetic acid. Inorganic oY~; 7ing agents can likewise be used in the presence of an acid, eg. sulfuric acid.
The concentration of r~Y;rl;7;nq agent in the aqueous or organic solution is customarily from 0.001 to 596 by weight, preferably ~rom 0 . 01 to 1% by weight, in each case based on the weight of the solution.
BASF Aktiengesellc-h-ft 930541 O.Z. 0050/44978 7 21 ~3887 If aqueous solutions of inorganic oxidizing agents are used, the amount of acid can remain limited to small amounts, f or example a f ew drops .
5 If organic oxidizing agents are used, the amount of the acid used, for example from 5 to 30% strength by weight aqueous acetic acid, is larger, since the water present in the acid serves as aqueous phase. In this case it is advisable to choose the amount of aqueous acid so that it c.lLL =,~,~J..ds approximately to the 10 amount of the hydrocarbon to be tested.
It is accordingly generally sufficient to treat from about 1 to 5 ml of the hydrocarbon marked according to the present invention with from 2 to 10 ml of a solution of an organic nY;~i7;n~ agent 15 in an organic solvent and from 1 to 5 ml of aqueous acid or with from 1 to 5 ml of an aqueous solution of an inorganic nlri~7in~
agent, optionally in the presence of an acid, at from 10 to 100 C, preferably from 20 to 80 C, in order that the color reaction may be obtained. This treatment advantageously takes the form of 20 extracting the hydrocarbon phase with the aqueous phase.
The leuco triarylmethanes to be used according to the present invention are readily obtainable and readily soluble in hydro-carbons. Moreover, they are simple to detect in that even very 25 small amounts of marker are rendered visible by a strong color reaction .
The Examples which follow illustrate the invention.
30 Example 1 2 ml of a solution of 10 ppm of leuco crystal violet in xylene were admixed with 3.5 ml of a solution of 50 ppm of 2,3--dichloro-5,6--dicy~nnhpn7oquinone in xylene and, after a 35 minute, the mixture was shaken up with 2 ml of 20% strength by weight acetic acid until the dye was completely dissolved in the aqueous phase. The aqueous phase has a deep violet color.
Example 2 2 ml of a solution of 10 ppm of leuco malachite green in xylene were admixed with 3.5 ml of a solution of 50 ppm of 2,3--dichloro-5,6--dicy~nnhPn7oquinone in xylene and, after a minute, the mixture was shaken up with 2 ml of 20% strength by 45 weight acetic acid until the dye was completely dissolved in the aqueous phase. The aqueous phase has a deep green color.
BASF Aktie~ 3. F~ chaft 930541 O.Z. 0050/44978 , 1 8 21 93&87 Example 3 2 ml of a solution of 10 ppm of leuco crystal violet in commer-cial diesel fuel were admixed with 3.5 ml of a 0.0~ strength by 5 weight solution of 2,3--dichloro-5,6--dicy~n~h~n7oquinone in xylene and, after a minute, the mixture was shaken up with 2 ml of 20%
strength by weight acetic acid until the dye was completely dis-solved in the aqueous phase. The aqueous phase has a deep violet color .
Example, 4 2 ml of a ~olution of 10 ppm of leuco malachite green in commer-cial diesel fuel were admixed with 3.5 ml of a 0.05% strength by 15 weight solution of 2,3--dichloro-5,6--dicy~n~hsn7cquinone in xylene and, after a minute, the mixture was shaken up with 2 ml of 20~
strength by weight acetic acid until the dye was completely dis-solved in the aqueous phase. The agueous pha~9e has a deep green color .
Example 5 2 ml of a 0.1~ strength by weight solution of leuco crystal violet in toluene were shaken up with 1. 5 ml of 0 .1~ strength by 25 weight aqueous iron( III ) chloride solution for 15 sec and heated to 70 C. The aqueous phase is observed to have a distinct bluish violet color.
Example 6 2 ml of a 0.1~ strength by weight solution of leuco crystal violet in toluene were shaken up with 1.5 ml of 0.196 strength by weight aS~ueous sodium peroxodisulfate solution for 15 sec and heated to 70 C. The aqueous phase is observed to have a distinct 35 bluish violet color.
Example 7 2 ml of a 0.1~ strength by weight solution of leuco crystal 40 violet in toluene were shaken up with 1.5 ml of 0.1% strength by weight aqueous potassium p~rr~n~snAte solution and 2 drops of 10 strength by weight sulfuric acid for 15 sec. The color of the potassium p~srr-n~n~te disappeared and the aqueous phase took on a distinct bluish violet color.
BASF Akti~ s^llc~~h~ft g30541 O.Z. 0050/44978 .. .
Example 8 2 ml of a 0.1% strength by weight solution of leuco crystal violet in toluene, 1.5 ml of 0.1% strength by weight aqueous 5 potassiu~ permanganate solution and 2 drops of 10% strength by weight sulfuric acid were shaken up for 15 sec and heated to 70 C.
The aqueous phase is observed to have a distinct bluish violet color .
Rl I
--CEI/¢~N~ R2 (I), ~ N~
where 20 z i8 substituted or unsubstituted phenyl, substituted or unsub-stituted naphthyl or a radical of the formula ~ , where y Y is Cl--Cl~alkyl, and 30 Rl, R2, R3 and R4 are identical or different and each i8 indepen-dently of the others hydrogen, Cl--Cl6--alkyl with or without interrupt~on by f rom 1 to 4 oxygen atoms in ether f unction and with or without substitution, substituted or unsubsti-tuted phenyl or substituted or unsubstituted naphthyl, as markers for hydrocarbons, to hydrocarbons comprising the abovementioned leuco triarylmethanes, and to a method f or detec-ting leuco triarylmethanes in hydrocarbons.
40 It is an object of the present invention to provide ~ovel markers for hydrocarbons. ~he novel markers should be readily obtainable and soluble in hydrocarbons. They should also be simple to detect; spPr;f;--~11y~ even very small amounts of markers should be v;c;h11i7~hl~ through a strong color reaction.
BASF Aktieng~c~llcrh~ft 930541 O.Z. 0050/44978 a We have found that this object is achieved by the above-defined leuco triarylmethanes of the formula I.
Any alkyl appearing in the formulae mentioned herein may be 5 straight-chain or branched.
In any 6ubstituted phenyl or naphthyl appearing in the formulae mentioned herein the number of ~ubstituents is generally from 1 to 3.
Substituted phenyl or naphthyl Z may have as substituents for example C1~16--alkyl, C1--C1~alkoxy, halogen, amino or mono--or di ( Cl--C16--alkyl ) amino .
15 Any substituted phenyl or naphthyl R1, R2, R3 or R4 may have as substituents for example C1--C16--alkyl with or without interruption by from 1 to 4 oxygen atoms in ether function, Cl--C16--alkoxy or phenoxy .
20 Substituted C1--C16--alkyl R1, R2, R3 or R4 may have as substituents for example hydroxyl, halogen or cyano. The number of sub-stituents is generally 1 or 2.
R1, R2, R3, R4 and Y are each for example methyl, ethyl, propyl, 25 isopropyl, butyl, isobutyl, sec--butyl, pentyl, isopentyl, neo-pentyl, tert--pentyl, hexyl, 2--methylpentyl, heptyl, octyl, 2~thylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3, 5, 5, 7--tetramethylnonyl, i5 otri-decyl, tetradecyl, pentadecyl or hexadecyl ~ the above designa-30 tions isooctyl, isononyl, 1sodecyl and isotridecyl are trivialnames derived from the oxo process alcohols -- cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edltion, Vol. A1, pages 290 to 293, and Vol. A lO, pages 284 and 285).
35 R1, R2, R3 and R4 may each also be ~or example 2~ethoxyethyl, 2~thoxyethyl, 2--propoxyethyl, 2--is LI~LU~O~LY :thyl, 2--butoxyethyl, 2-- or 3--methc,.~y~L-,~yl, 2-- or 3~thoxypropyl, 2-- or 3--propoxy-propyl, 2-- or 3--butoxypropyl, 2-- or 4--methoxybutyl, 2-- or 4~thoxybutyl, 2--or 4--~L~ YbU~Y1~ 3,6~ioxaheptyl, 3,6--dioxy-40 octyl, 4, 8--dioxanonyl, 3, 7--dioxaoctyl, 3, 7~ioxanonyl, 4, 7--dioxa-octyl, 4,7--dioxanonyl, 2--or 4--butoxybutyl, 4,8--dioxadecyl, 4~ 7~?~ n~ n~ . yl~ 3, 6, 9--trioxadecyl, 3, 6, 9--tr~ r yl, 3,6,9--tri~Y~t3n~l~cyl, 4,7,10--tr~nY~Iln~1~cyl~ 3,6,9,12--LeLLc~v~LLi--decyl, 3, 6, 9, 12--tetraoxatetradecyl, 2--hydL~--y~Lhyl, 2--chloro-45 ethyl, 2--cyanoethyl, 2--or 3--IIYdL~ Y~ Y1~ 2--or 3--chloropropyl,2-- or 3--cyanopropyl, 2--or 4--lly ILo~ybuLyl~ 2-- or 4--chlorobutyl, _ _ . . . .. .. . _ . _ .. . ... . .. _ _ . _ . . . .
BASF Aktiengese~ rha~t 930541 O.Z. 0050/44978 3 2~ 93887 2-- or 4--cyanobutyl, 5--hydroxypentyl, 5--chloropentyl, 5~yano-pentyl, 6--hydroxyhexyl, 5--chlorohexyl or 6--cyanoheYyl.
Suitable substituents for Z, as well as the aforementioned 5 C1--C16--alkyl radicals, include for example fluorine, chlorine, bromine, mono-- or dimethylamino, mono-- or diethylamino, mono-- or dipropylamino, mono-- or diisopropylamino, mono-- or dibutylamino, mono--or dipentylamino, mono-- or dihexylamino, mono-- or diheptyl-amino, mono--or dioctylamino, mono-- or bis(2--ethylhexyl~amino, 10 mono--or dinonylamino, mono--or didecylamino, mono-- or diundecyl-amino, mono-- or didodecylamino, mono-- or ditridecylamino, mono--or ditetradecylamino, mono- or dipentadecylamino, mono-- or ~1~ hpy~A~r-ylamino~ N--methyl-N--ethylamino, methoxy, ethoxy, propoxy, is~ p-~Ay~ butoxy, isobutoxy, sec--butoxy, pentyloxy, 15 isopentyloxy, neopentyloxy, tert--pentyloxy, hexyloxy, 2--methyl-pentyloxy, heptyloxy, octyloxy, 2--ethylhexyloxy, isooctyloxy, nonyloxy, isononyloxy, decyloxy, isodecyloxy, undecyloxy, dodecyloxy, tridecyloxy, 3,5,5,7--tetramethylnonyloxy, isotri-decyloxy, tetradecyloxy, pentadecyloxy or hexadecyloxy.
Preference for marking hydrocarbons is given to the use of leuco triarylmethanes of the formula I where Z i~3 substituted or unsub-~tituted phenyl.
25 Preference for marking hydrocarbons is further given to the use of leuco triarylmethanes of the formula I where R1, R2, R3 and R~
are each i nrl~rp~s~ntly of the others Cl--C6--alkyl .
Particular preference for the marking of hydrocarbons is given to 30 the use of leuco triarylmethanes of the formula II
Rl ~ CE~ N~ R2 [~ (II), R3~ ~ R4 where X is hydrogen, amino or mono-- or di(C1--C16--alkyl)amino and R1, R2, R3 and R~ are each as defined above.
45 Very particular preference for the marking of hydrocarbons is given to the use of leuco triarylmethanes of the formula II where X is hydrogen or di(Cl--C6--alkyl)amino, PCp~ y dimethylamino, _ _ _ , . , ,, . ,, , , _ _ ,, _ ,,,, , ,,, _ _ _ _ _ _ _ BASF ~l~ti-~n~c~llcchaft 930541 O.Z. 0050/44978 and Rl, R2, R3 and R4 are each ;n~lQr~n~Qrltly of the others Cl~alkyl, especially methyl.
The leuco triarylmethanes of the formula I are known per se and 5 ~IQ~rr~hed for example in 1~. Venkataraman, The Chemistry of Synthetic Dyes, Vol. II, Academic Press, New York, 1952, or can be obtained for example by the methods mentioned therein.
The leuco triarylmethane of the formula II where X is hydrogen 10 and R1, R2, R3 and R4 are each methyl is leuco malachite green, while the leuco triarylmethane of the formula II where X is dimethylamino and Rl, R2, R3 and R4 are each again methyl is leuco crystal violet.
15 Marking for the purposes of the present invention is the addition to hydrocarbons of the leuco triarylmethanes of the formula I in such a concentration that, to the human eye, the hydrocarbons have barely any or no visible color, but the leuco triaryl-methanes o~ the formula I are readily and distinctly visibly 20 detectable by the methods of detection more particularly described herein.
The present invention further provides hydrocarbons containing one or more o~ the leuco triarylmethanes of the formula I. The 25 cvl.cel,~Lation of the leuco triarylmethanes of the formula I in the hydrocarbons is generally from 1 to 500 ppm, preferably from 5 to 50 ppm, especially about 40 ppm.
Hydrocarbons for the purposes of the present invention are 30 aliphatic or aromatic hydrocarbons which are liquid under standard conditions, for example pentane, hexa~le, heptane, octane, isooctane, benzene, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, diisopropylnaphthalene, chlorobenzene or dichlorobenzene. More particularly, they are 35 mineral oils, for example motor fuels, such as gasoline, kerosine or diesel fuel, or oils, such as heating oil or engine oil.
The leuco triarylmethanes of the formula I are especially suitable for marking mineral oils where some form of marking is 40 mandatory, for example for tax reasons. To keep the costs for this to a minimum, it is desirable to keep the amount of marker used to a minimum.
To mark hydrocarbons, the leuco triarylmethanes of the formula I
45 are used either without a solvent or in the form of solutions.
Suitable solvents are organic solvents. Preference is given to using aromatic hydrocarbons, such as toluene, xylene, , . ... _ .. _ .. ... .. , , , _ _ _ _ BASF ~l~ti ,~llschaft 930541 O.Z. 0050/44978 dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatlcs available from Shell as Shellsol(~) A3. To avoid the re-sulting solution having a high viscosity, the concentration of leuco triarylmethane I chosen for the solution generally ranges 5 from 20 to 80% by weight, based on the solution.
The solubility may be improved by using ~urther, co-solvents, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, 10 octanol, 2--ethylhexanol or cyclohexanol, glycols, such as butyl-ethylene glycol or methylpropylene glycol, amines, such as triethylamine, diisooctylamine, dicyclohexylamine, aniline, N--methylaniline, N,N--dimethylaniline, toluidine or xylidine, AlkAn~r~in~ such as 3--(2--methoxyethoxy)propylamine, o-cresol, 15 m--cresol or p-cresol, ketones, such as diethyl ketone or cyclo-hexanone, lactones, such as y--butyrolactone, carbonates, such as ethylene carbonate or propylene carbonate, phenols, such as t--butylphenol or nonylphenol, esters, such as methyl phthalate, ethyl phthalate, 2--ethylhexyl phthalate, ethyl acetate, butyl 20 acetate or cyclohexyl acetate, amides, such as N,N--dimethyl-formamide, N,N--diethylacetamide or N--methylpyrrolidone, or mixtures thereof.
The leuco triarylmethanes of the formula I to be used according 25 to the present invention permit very simple detection of marked hydrocarbons, even if, as mentioned above, the marker substances are present only in a concentration o~ about 10 ppm or less.
In some ca3es it is also advantageous for the marker to be used 30 to comprise mixtures between leuco triarylmethanes of the formula I.
The presence in hydrocarbons of the leuco triarylmethanes of the formula I used as markers is advantageously detected on treating 35 the marked hydrocarbon with an oY; ~ ; n~ agent and optlonally a protic acid in the presence of water.
This treatment gives rise to a clearly visible color rRaction and the leuco triarylmethane I forms a triarylmethane dye and trans-40 fers to the aqueous phase.
The resulting triarylmethane dye conforms to the formula III
BA'SF Aktieng~c~llc~-hAft 930541 O.Z. 0050/44978 1 6 21 93&87 C~N~ R2 ~n~
1 (III), ~ N~ 4 where Z, Rl, R2, R3 and R4 are each as defined above and An~ is the equivalent of an anion (eg. sulfate, hydrogensulfate, phos-phate, hydL~,g~llphc,~hate, di~lyd~gt~ hosphate~ nitrate, acetate, 15 lactate or citrate).
Suitable ~Y; ~; 7; nq agents include for example customary, inorganic or organic ~Y;ri;7;ns agents known per se, such as alkali metal r~r~~n~n~tes~ eg. potassium permanganate, ammonium 20 dichromate, alkali metal dichromates, eg. sodium or potassium dichromate, ; peroxodisulfate, alkali metal peroxo-disulfates such as sodium or potassium peroxodisulfate, potas3ium pe~ sulfate, iron(III) salts, eg. iron(III) chloride or iron(III) sulfate, hydrogen peroxide (in combination with 25 suitable catalysts ), quinones, eg . 2, 3--dichloro-5, 6--dicyanobenzo-quinone or 2, 3, 5, 6--tetrachlorobenzoquinone, sodium perborate or cerium(IV) salts, eg. cerium(IV) sulfate.
~oronlling on the nature of the nYi~7;n~ agents, they can be used 30 either in the form of an aqueous solution (inorganic ~Y;~;7;
agents) or in the form of a solution in an organic solvent (organic ~Y;~;7;n~ agents~. Suitable organic solvents include for example toluene, xylene, cy~r,hFY~n~n~, acet~honnn~, y--butyro-lactone, 2--ethylhexyl acetate or esters of phthalic acid.
If organic ~Y;~l;7;nq agent~ are used, a dilute aqueous acid is employed, for example from 5 to 30~ strength by weight aqueoua acetic acid. Inorganic oY~; 7ing agents can likewise be used in the presence of an acid, eg. sulfuric acid.
The concentration of r~Y;rl;7;nq agent in the aqueous or organic solution is customarily from 0.001 to 596 by weight, preferably ~rom 0 . 01 to 1% by weight, in each case based on the weight of the solution.
BASF Aktiengesellc-h-ft 930541 O.Z. 0050/44978 7 21 ~3887 If aqueous solutions of inorganic oxidizing agents are used, the amount of acid can remain limited to small amounts, f or example a f ew drops .
5 If organic oxidizing agents are used, the amount of the acid used, for example from 5 to 30% strength by weight aqueous acetic acid, is larger, since the water present in the acid serves as aqueous phase. In this case it is advisable to choose the amount of aqueous acid so that it c.lLL =,~,~J..ds approximately to the 10 amount of the hydrocarbon to be tested.
It is accordingly generally sufficient to treat from about 1 to 5 ml of the hydrocarbon marked according to the present invention with from 2 to 10 ml of a solution of an organic nY;~i7;n~ agent 15 in an organic solvent and from 1 to 5 ml of aqueous acid or with from 1 to 5 ml of an aqueous solution of an inorganic nlri~7in~
agent, optionally in the presence of an acid, at from 10 to 100 C, preferably from 20 to 80 C, in order that the color reaction may be obtained. This treatment advantageously takes the form of 20 extracting the hydrocarbon phase with the aqueous phase.
The leuco triarylmethanes to be used according to the present invention are readily obtainable and readily soluble in hydro-carbons. Moreover, they are simple to detect in that even very 25 small amounts of marker are rendered visible by a strong color reaction .
The Examples which follow illustrate the invention.
30 Example 1 2 ml of a solution of 10 ppm of leuco crystal violet in xylene were admixed with 3.5 ml of a solution of 50 ppm of 2,3--dichloro-5,6--dicy~nnhpn7oquinone in xylene and, after a 35 minute, the mixture was shaken up with 2 ml of 20% strength by weight acetic acid until the dye was completely dissolved in the aqueous phase. The aqueous phase has a deep violet color.
Example 2 2 ml of a solution of 10 ppm of leuco malachite green in xylene were admixed with 3.5 ml of a solution of 50 ppm of 2,3--dichloro-5,6--dicy~nnhPn7oquinone in xylene and, after a minute, the mixture was shaken up with 2 ml of 20% strength by 45 weight acetic acid until the dye was completely dissolved in the aqueous phase. The aqueous phase has a deep green color.
BASF Aktie~ 3. F~ chaft 930541 O.Z. 0050/44978 , 1 8 21 93&87 Example 3 2 ml of a solution of 10 ppm of leuco crystal violet in commer-cial diesel fuel were admixed with 3.5 ml of a 0.0~ strength by 5 weight solution of 2,3--dichloro-5,6--dicy~n~h~n7oquinone in xylene and, after a minute, the mixture was shaken up with 2 ml of 20%
strength by weight acetic acid until the dye was completely dis-solved in the aqueous phase. The aqueous phase has a deep violet color .
Example, 4 2 ml of a ~olution of 10 ppm of leuco malachite green in commer-cial diesel fuel were admixed with 3.5 ml of a 0.05% strength by 15 weight solution of 2,3--dichloro-5,6--dicy~n~hsn7cquinone in xylene and, after a minute, the mixture was shaken up with 2 ml of 20~
strength by weight acetic acid until the dye was completely dis-solved in the aqueous phase. The agueous pha~9e has a deep green color .
Example 5 2 ml of a 0.1~ strength by weight solution of leuco crystal violet in toluene were shaken up with 1. 5 ml of 0 .1~ strength by 25 weight aqueous iron( III ) chloride solution for 15 sec and heated to 70 C. The aqueous phase is observed to have a distinct bluish violet color.
Example 6 2 ml of a 0.1~ strength by weight solution of leuco crystal violet in toluene were shaken up with 1.5 ml of 0.196 strength by weight aS~ueous sodium peroxodisulfate solution for 15 sec and heated to 70 C. The aqueous phase is observed to have a distinct 35 bluish violet color.
Example 7 2 ml of a 0.1~ strength by weight solution of leuco crystal 40 violet in toluene were shaken up with 1.5 ml of 0.1% strength by weight aqueous potassium p~rr~n~snAte solution and 2 drops of 10 strength by weight sulfuric acid for 15 sec. The color of the potassium p~srr-n~n~te disappeared and the aqueous phase took on a distinct bluish violet color.
BASF Akti~ s^llc~~h~ft g30541 O.Z. 0050/44978 .. .
Example 8 2 ml of a 0.1% strength by weight solution of leuco crystal violet in toluene, 1.5 ml of 0.1% strength by weight aqueous 5 potassiu~ permanganate solution and 2 drops of 10% strength by weight sulfuric acid were shaken up for 15 sec and heated to 70 C.
The aqueous phase is observed to have a distinct bluish violet color .
Claims (6)
1. The use of leuco triarylmethanes of the formula I
(I), where Z is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl or a radical of the formula , where Y is C1-C16-alkyl, and R1, R2, R3 and R4 are identical or different and each is independently of the others hydrogen, C1-C16-alkyl with or without interruption by from 1 to 4 oxygen atoms in ether function and with or without substitution, substi-tuted or unsubstituted phenyl or substituted or unsubsti-tuted naphthyl, as markers for hydrocarbons.
(I), where Z is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl or a radical of the formula , where Y is C1-C16-alkyl, and R1, R2, R3 and R4 are identical or different and each is independently of the others hydrogen, C1-C16-alkyl with or without interruption by from 1 to 4 oxygen atoms in ether function and with or without substitution, substi-tuted or unsubstituted phenyl or substituted or unsubsti-tuted naphthyl, as markers for hydrocarbons.
2. A use as claimed in claim 1 wherefor Z is substituted or un-substituted phenyl.
3. A use as claimed in claim 1 wherefor R1, R2, R3 and R4 are each independently of the others C1-C6-alkyl.
4. A use as claimed in claim 1 wherefor the leuco triaryl-methanes of the formula I have the formula II
( II ), where X is hydrogen, amino or mono- or di(C1-C16-alkyl)amino and R1, R2, R3 and R4 are each as defined in claim 1.
( II ), where X is hydrogen, amino or mono- or di(C1-C16-alkyl)amino and R1, R2, R3 and R4 are each as defined in claim 1.
5. A hydrocarbon with a marker comprising one or more leuco triarylmethanes of the formula I as set forth in claim 1.
6. A method for detecting the presence of a leuco triarylmethane of the formula I as set forth in claim 1 in a hydrocarbon, which comprises treating the marked hydrocarbon with an oxidizing agent and optionally a protic acid in the presence of water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4422336A DE4422336A1 (en) | 1994-06-27 | 1994-06-27 | Use of leukotriarylmethanes for marking hydrocarbons |
| DEP4422336.6 | 1994-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2193887A1 true CA2193887A1 (en) | 1996-01-04 |
Family
ID=6521536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002193887A Abandoned CA2193887A1 (en) | 1994-06-27 | 1995-06-16 | Use of leucotriarylmethanes for marking hydrocarbons |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0767822A1 (en) |
| JP (1) | JPH10502170A (en) |
| AU (1) | AU2793195A (en) |
| BR (1) | BR9508145A (en) |
| CA (1) | CA2193887A1 (en) |
| CZ (1) | CZ381196A3 (en) |
| DE (1) | DE4422336A1 (en) |
| FI (1) | FI965197A (en) |
| HU (1) | HUT76518A (en) |
| NO (1) | NO965612L (en) |
| PL (1) | PL317997A1 (en) |
| TR (1) | TR199500758A2 (en) |
| TW (1) | TW287195B (en) |
| WO (1) | WO1996000272A1 (en) |
| ZA (1) | ZA955266B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6120536A (en) * | 1995-04-19 | 2000-09-19 | Schneider (Usa) Inc. | Medical devices with long term non-thrombogenic coatings |
| US6099562A (en) | 1996-06-13 | 2000-08-08 | Schneider (Usa) Inc. | Drug coating with topcoat |
| US5980972A (en) * | 1996-12-20 | 1999-11-09 | Schneider (Usa) Inc | Method of applying drug-release coatings |
| US8236048B2 (en) | 2000-05-12 | 2012-08-07 | Cordis Corporation | Drug/drug delivery systems for the prevention and treatment of vascular disease |
| US6776796B2 (en) | 2000-05-12 | 2004-08-17 | Cordis Corportation | Antiinflammatory drug and delivery device |
| WO2002026139A1 (en) | 2000-09-29 | 2002-04-04 | Cordis Corporation | Coated medical devices |
| US8182527B2 (en) | 2001-05-07 | 2012-05-22 | Cordis Corporation | Heparin barrier coating for controlled drug release |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB357179A (en) * | 1930-06-17 | 1931-09-17 | Patent Fuels & Color Corp | Improvements in the art of colouring gasoline or other petroleum distillates |
| US1997670A (en) * | 1932-06-21 | 1935-04-16 | George L Armour | Method of and means for identifying brands of liquid hydrocarbons |
| US2063575A (en) * | 1934-03-31 | 1936-12-08 | Standard Oil Co | Dispersing of phenolphthalein in mineral lubricating oils |
| US2755203A (en) * | 1954-02-03 | 1956-07-17 | Du Pont | Process of converting a polyamino-triarylmethane dye coating on a base from a stabilized leuco form to a colored form |
| DE2723774A1 (en) * | 1977-05-26 | 1978-11-30 | Bayer Ag | PROCESS FOR THE RECOVERY OF TRIARYLMETHANE DYES |
| AU8928382A (en) * | 1981-10-19 | 1983-04-28 | Matsushita Electric Industrial Co., Ltd. | Dye composition |
| DE3815605A1 (en) * | 1988-05-06 | 1988-10-20 | Alfred Dr Rer Nat Flath | Use of additive mixtures as a means for increasing the vaporisation rate and combustion rate and the combustion stability of liquid propellants and fuels injected into rocket combustion chambers or high-output combustion installations |
| DE4001662A1 (en) * | 1990-01-22 | 1991-07-25 | Basf Ag | Marking mineral oil with basic dyestuff contg. at least 2 amino gps. - undergoes bathochromic shift and increase in extinction on adding protonic acid |
| EP0486749A1 (en) * | 1990-11-22 | 1992-05-27 | Hodogaya Chemical Co., Ltd. | Triarylmethane compounds and pressure sensitive recording material |
-
1994
- 1994-06-27 DE DE4422336A patent/DE4422336A1/en not_active Withdrawn
-
1995
- 1995-06-16 WO PCT/EP1995/002341 patent/WO1996000272A1/en not_active Application Discontinuation
- 1995-06-16 EP EP95923337A patent/EP0767822A1/en not_active Withdrawn
- 1995-06-16 PL PL95317997A patent/PL317997A1/en unknown
- 1995-06-16 AU AU27931/95A patent/AU2793195A/en not_active Abandoned
- 1995-06-16 CZ CZ963811A patent/CZ381196A3/en unknown
- 1995-06-16 CA CA002193887A patent/CA2193887A1/en not_active Abandoned
- 1995-06-16 BR BR9508145A patent/BR9508145A/en not_active Application Discontinuation
- 1995-06-16 HU HU9603589A patent/HUT76518A/en unknown
- 1995-06-16 JP JP8502764A patent/JPH10502170A/en active Pending
- 1995-06-21 TW TW084106393A patent/TW287195B/zh active
- 1995-06-26 ZA ZA955266A patent/ZA955266B/en unknown
- 1995-06-27 TR TR95/00758A patent/TR199500758A2/en unknown
-
1996
- 1996-12-23 FI FI965197A patent/FI965197A/en unknown
- 1996-12-27 NO NO965612A patent/NO965612L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO965612L (en) | 1997-02-21 |
| HU9603589D0 (en) | 1997-02-28 |
| BR9508145A (en) | 1997-11-04 |
| EP0767822A1 (en) | 1997-04-16 |
| FI965197A (en) | 1997-02-19 |
| JPH10502170A (en) | 1998-02-24 |
| AU2793195A (en) | 1996-01-19 |
| DE4422336A1 (en) | 1996-01-04 |
| WO1996000272A1 (en) | 1996-01-04 |
| CZ381196A3 (en) | 1997-06-11 |
| FI965197A0 (en) | 1996-12-23 |
| PL317997A1 (en) | 1997-05-12 |
| NO965612D0 (en) | 1996-12-27 |
| ZA955266B (en) | 1996-12-27 |
| TR199500758A2 (en) | 1996-06-21 |
| HUT76518A (en) | 1997-09-29 |
| TW287195B (en) | 1996-10-01 |
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