GB2344599A - Method for marking liquids and compounds for use in said method - Google Patents
Method for marking liquids and compounds for use in said method Download PDFInfo
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- GB2344599A GB2344599A GB9905117A GB9905117A GB2344599A GB 2344599 A GB2344599 A GB 2344599A GB 9905117 A GB9905117 A GB 9905117A GB 9905117 A GB9905117 A GB 9905117A GB 2344599 A GB2344599 A GB 2344599A
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- heterocyclic
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Classifications
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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
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
- C10L1/233—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
A method of marking liquids, particularly fuels, comprising the steps of adding a photochromic compound to the liquid and exposing the liquid to ultraviolet light to increase the visibility of the photochromic compound whereby the colour or intensity of the compound after exposure to the ultraviolet light acts as an identification marker for the liquid. Suitable photochromic compounds include spiro-oxazines and heterocyclochromenes.
Description
.'itle : Method for marking liquids and compounds for use in said method.
DESCRIPTION
The present invention relates to an improved method for marking liquids and to compounds for use in the method In particular, the invention relates to a method for marking fuels.
Fuel samples are generally required to be labelled for a variety of purposes such as to distinguish between taxed and untaxed fuel oils or a brand identification for organic based liquids. Conventionally, fuels have been differentiated by means of colour, for example by including an appropriate dyestuffin the fuel, since colour is the simples way of idlerfying fuel either by eye or quantitatively using a spectophotometer.
The fuel is ideally marked with trace amounts of material ( < 50pp) such that the properties conferred by the marker chemical do not affect the bulk liquid. Additionally, the marker compounds must impart negligible cost to the liquid in the concentrations in which they are used and must not adversely affect the performance of the liquid. It sFuld also be possible to detect concentrations as low as 5% of the marker in fuel in cases were the fuel has been diluted with unmarked fuel.
A variety of compounds have been descnbed for marking fuels in the aforementioned manner. Often the fuel is marked with a clsmicK which is initially colourless but which becomes coloured upon the addition of a"developer"compound. A number of such systems have been developed which use traditional reagent based analytical tests and in which the undeveloped marker imposes no obvious colour on the fuel For example, US 5498808 describes the use of fluorescein esters that become highly fluorescent on treatment with strongly basic solutions. Carbonyl compounds may be detected by their reaction with pyrylium or indole compounds, as descnbed in WO 96/02613. Alively, WO 95/07460 relies on the reaction of stable diazonium salts with aromatic amines for this purpose. Other compounds become visibly coloured on the addition of acid or base, see for example, EP 0438734, WO 95/00606, US 5205840 and WO 95/10581.
In all of the aforementioned examples, the chemical properties of the marker compound when included in the fuel must be dieret in at least one respect from the properties of the fuel and must react rapidly enough for convenient identincation of the fuel
All require the addition of a reagent to the marker-fuel mixture to enable detection of the marker and generally result in permanent changes occurrmg to the mixture.
The aim of the present invention is to provide an improved method for marking liquids.
Accordingly, the present invention provides a method of marking liquids comprising the steps of adding a photochromic compound to the liquid and exposing the liquid to ultraviolet light to increase the visiez of the photochromic compound whereby the colour or intensity of the compound aster exposure to ultra violet light acts as an identon marker for the liquid.
Pre & rably, the photochromic compound is added to the liquid to be marked at a concentration that imparts no visible colour to the liquid Preferably, the photochromic compound becomes visible upon exposure to the UV light.
The present invention is particularly suitable for marking fuels as the compounds recommended show stability therein and may be detected at sub-ppm levels.
Preferably, the liquid is cooled to a low temperatur during exposure to uv light to pie= maximum intensity of colour. Preferably, a temperature in the range of -100 to 45 C is providd, more preferably -80 to 25 C.
The absorbance of the photochromic compound used in the present invention is such that the absorbance on exposure to UV light under the appropriate temperature conditions is greater than 0.1, more preferably greater than 0.6, especially 0.8-1.
The marked liquid is preferably illuminated by an ultraviolet source or a uash lame, such as a photographic flash lamp. Preferably, the marked liquid is illuminated at a constant distance for a constant length of time at a specified temperature to ensure reproduci*7 of the colour formation thereby ensuring the correct identification of the liquid from the detected marker.
Preferably, the sample of liquid to be ideified is stored in a light free environment prior to exposure to ultraviolet light to ensure that any change in colour that has occurred in the marker during its exposure to ambient light is reversed prior to testing. Alternatively, the sample may be heated in a sealed vial to reverse the colour change prior to zonez The increased visw ofthe compound by exposure to the W light may be reversed by the removal of the LTV light source. For example, the method may comprise taking a sample of the liquid from the bulk liquid in a vial, if necessary cools to a specified temperature, exposing the sample to UV light to enable the detection of the compound and d thereby identify the liquid and returning the sample back to the bulk liquid. The change to the colourless state win then occur in the bulk liquid especially if it is in a 1 Eee envirorm.
Tbepbotocbromic compound is preferably provided as a liquid c-onte for addition to the liquid to be marked. Preferably, a concentrate of between 1% to 10% of the marker in an organic solvent is used. Organic solvents suitable for this purpose are, for example, alkyl benzenes, alkylnaphalenffl or a proprietary blend of such compounds. Polar organic solvents may be included to increase the solubility of the marker cowpound in the concentrate, such as formamide, N,N-dimethylformamide and N-methylprrolidone.
Preferably, the solvents are a miture of aromatic and aprotic solvents. These solvents may be used singly or in blends but must be miscible with the liquid being marked.
Preferably, the final concentration of the marker in the liquid is between 1ppm and 30ppm (w/vol) but the kvel win be dependent upon the inherent colour of the solvent used.
The method and compounds of the present invention may be provided in combination with other markers. For example, the photochromic compounds may be used in conjunction with existing solvem dyes, such as mono-and bis-azo dyes, quinohne, methine, xantbene, perylene and anmraquinone based dyes. Alternatively, the photochromic compounds may be used in combination with colourless marker chemicals often found in fuels which require alcaline conditions for the forion of colour in an extracted aqueous layer, such as qm coumarin and those covered by WO 96/32462 with both types of compound being detectable independently of one other. The photochromic compounds may also be used in combination with, or added as a mixture with, colourless marker chemicals which require acidic conditions for the formation of colour, such as basic azo dyes.
The present invention also provides a number of compounds for use in the method.
The pbotochromic compounds used in the method possess the ability to change colour or shade reversibly in light of a particular frequency or intensity. Compounds for use in the method of the present invention are preferably selected from the groups consisdng of spirooxazines (particularlybutnotexctusivespiro(indoiino)oxazines)andheterocycbchromenes, in particular benzopyrans or napthopyrans.
For example, spiro-oxazines of the following general formula may be used :
R2 R3 R4 I , A p ; N J wherein: R. s Ri is a hydrogen atom, a liner or branched alkyl, alkenyl, alkynyl, phenyl, phenylalkyl, mono-, di- or tri- substituted phenyl, alkoxy or alkoxyalkyl, carbocyclic, alkylcarbocyclic, heterocyclic or alkylbeterocydic ring and may be fused to ring A ;
R2 and R3 radependently represent a hydrogen atom, a liner or branched aIkyl, alkeayyl, carbocyclic or heterocyclic ring, phenyl, phenylalkyl such as benzyl, mono-, di-or tri- subsSuted phenyl and may together represent an aScyclic ring which may be further substituted with alkyl, aryl or heteroaryl groups and may inclue spiro carbons, norbornane andadamantane ;
R4 is a hydrogen atom, an alkyl, alkoxy, aryl, heteroaryl or ammo group;
Rs is hydrogen or an amine fiionalky of general formula-NRR", wherein each of
R' and R" independently represents a hydrogen atom or an alkyl, cycloalkyl or phenyl group or a substituted derivative thereof or an amine functionality which is a cyclobeteroakyl ring or a substituted cycloheteroalkyl ring whose ring includes one or more heteroatoms, or a group of formula -R, -Or, -SR, -COR or COOR wherein R represents a hydrogen atom, alkyl, aryl, or heteroaryl, or -Z, CH2Z, -CHZ2 or -CZ3 wherein Z represents a halogen or nitro, cyano or thiocyano group; or with R6 fmm a cyclo-group selected from a heterocyclic, optionally substituted, 5-membered ring or a six-membered carbocyclic or heterocyclic moiety, the hetero-atom being selected from O, S, Se, NH or NRr where Rr represents an alkyl group and may be fier substituted with alkyl, aryl, beteroaryl, carbocyclic or heterocyclic rings fused thereto and optional subsdtuents being selected from alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen, azo, imino, amide, ester, cyano, trinuoromethyl, nitro or dialkylamino groups ; or is selected from alkenyl, alkynyl, imino, azo, amino, carboxy ester, amide, cyano or troluoromethyl ; R6 is hydrogen or a group as defined above for R5; R is a group as defined above for Rs or when R5 and R6 form a six-mernbered carbocyclic or heterocyclic moiety is a group selected from aryl, heteroaryl, heterocyclic, alkenyl, alkenylaryl, cycloalkenyl, cycloalkenylaryl, alkynyl, alkynylaryl, iminoaryl, and azoaryl with a linkage to at least one ammo or alkoxy group ; or when Rs and R6 form a cyclo-group as defined above is a group of the formula NRxRy in which Rx and Ry may be the same or dirent and may include alkyl, carbocyclic, aryl or heterocychc groups or may be part of a heterocyclic ring together with the nitrogen atom to which they are attached, this ring possessing one or more heteroatoms and which in turn may bear further a ! kyl, fused aryl or heteroaryl groups;
R8 is a group as defined above for Rs or when Rs and R6 form a cyclo-group as defined above is a hydrogen atom or a substituent selected from alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen, azo, imino, amide, ester, cyano, trifluoromethyl, nitro or dialkylammo groups or when Rs and R6 form a six-membered carbocyclic or heterocyclic moiety is a group selected from hydrogen, alkyl, alkoxy, alkenyl, alkynyl, imino, azo, amino, carboxy ester, amide, cyano, halogen, triuoromedlyl, nitro, aryl or heteroaryl ;
and Ring"A"is a carbocyclic, heterocyclic or benzene ring which is substituted by a group (R9)n, n being an integer between 0 and 4, RS being a hydrogen atom or an amine functionality of general formula-NRR"as defined above with reference to R5, a group of formula-R,-OR,-SR,-COR or COOR wherein R represents a hydrogen atom, alkyl, aryl, or heteroaryl, or-Z, CHZ,-CHZ2 or-CZ3 wherein Z represents a halogen or nitro, cyano or thiocyano group, or an alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen, azo, imino, amide, ester, cyano, trifluoromethyl, nitro or dialkylamino group or Ring A may optionally have a carbocyclic or heterocyclic rmg fused to it.
The synthesis and exemples of the spiro-(indolino) oxazine compounds are described in
US 4913544, including a full list of the permutations of the subies, the contents of which are incorporated herein by reference. Further compounds are also described in European
Patent No. s 0600667-9, WO 95/05385 and US 4851530 the contents of which are also incorporated herein ty reiiwce.
A preferred spiro-oxazine compound for use in the method of the present invention has the formula:
Benzopym are a fir class of photochromic compounds that may be employed in the method of the present invention. For example, having the general formula :
wherein:
R10 may represent a nvemsmberedheterocyctic group containmg one or more heteroatoms and fused either to the f-face or the g-face of the benzo moiety of the benzopyran such that the heteroatom in the heterocycle is fused directly to to carbon carbon atom the benzo moiety and optionally the fused heterocyclic group can have in turn a further carbocyclic group, heterocyclic group of a group of formula R13 as defined below, R11 and R12 may independently represent a carbocyclic or heterocyclic group or taken with the intervening carbon may be part of a carbocyclic or heterocyclic ring system ;R13 may represent a hydrogen atom or a substituent selected from alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen, substituted or ; msubstituted amino, azo, imino, amide, ester, cyano, trifluoromethyl or nitro groups.
Further subsdtuents and examples of suitable benzopyrans can be found in WO 95/05382, the contents of which are incorporated herein by reference.
Naphttopyrans may also be used in the method of the present invention. For example, compounds having the general formula :wherein:
R'd represents a group of formula -NR15R16 wherein each of R15 and R16 represent represent alkyl, carbocyclic or heterocyclic groups, or when taken with the intervening nitrogen atom to which they are attached a heterocyclic ring havig one or more heteroatoms and which may optionally carry at least one substituent selected from alkyl, aryl or heteroaryl groups; R17 and R18 independently represent alkyl, carbocyclic or heterocyclic groups which may bear further alkyl, alkenyl, carbocyclic or heterocychc groups as substitutents, or when taken together with the intervening carbon atom to which they are attached a carbocyclic or heterocyclic ring; R19 represents a hydrogen atom, alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen, a group of formula R14 as described above, azo, imino, amide, carboxylate, ester, cyano, trifuoromethyl or nitro, or additionally R19 may represent a carbocyclic or heterocyclic ring fused to ring C. R14 may alternatively represent an alkoxy or aryloxy group and R19 can additionally be an amino group.
Examples of semble naphthopyrans can be found in WO 94/22850 and WO 95/05371, the contents of which are incorporated herein by reference.
A preferred naphthopyran for use in the method of the present invention has the formula:
The present invention win now be further described in relation to the following
Examples and Figures 1 and 2 of the accompanying drawings in which Figure 1 is the molecular structure of the photochromic compound 6'-indolino-1-isobutyl-3,3-dimethylspiro (indolim-2, 3'-3H-naphthol [2,1-b][1, 4] oxazine]; and Figure 2 is the molecular structure of the p3chromic compound 3-phenyl-3-(4'-N-piperidinyl)phenyl)-6-morpholino-3H naphtbo l-b] pyraIL Example 1.
A concentrate of 1% by weight of the photochromic compound 6'-indoline-l-isobutyl- 3, 3-dimethylspiro (indoline-2, 3'-3H-naphthol [2, 1-b] [1, 4] oxazin was prepared using a blend of aromatic solvents and a polar aprotic solvent. The compound was added to fuels at a level of 1-10 ppm (w/vol) and exhibited an absorbance of up to 0.8 by irradiation of a lOppm solution with a standard laboratory 30W near ultraviolet lamp at about 0 C in kerosene (ex
Conoco). This photochromic compound (see Figure 1) exhibits one of the strongest colour intensities for such compounds at ambient temperatures for a given degree of irradiation and a reasonable solubility.
Example 2.
A concentrate of the photochromic compound 3-phenyl-3-(4'-(N-piperidinyl)phenyl) 6-morpholino-3H-naphtho [2, 1-b] pyran (see Figure 2) was added to fuels at a level of 5-30 ppm (w/voD and exhibited an absorbance of around 0.7 by irradiation of a 20 ppm solution in kerosene (ex. Conoco) with a standard laboratory 30W near ultraviolet lamp at around 0 C.
The use of photochromic compounds in the method of the present invention enables detection of a marker chemical in a liquid without the addition of further chemical reagents which is time consuming, cretes waste and is poteniallv hazardous. The method of the present invention also enables the reversal of changes made to the marked chemical without the addition of fier chemical reagents. A wide range of photochromic compounds are available which wil be suitable for marking liquids, the choice of compound bein dependent upon the colour and shade of the liquid to be marked.
The photochromic compounds may also be used in conjunction with existing solvent dyes so providing additional means for idedfication for a fuel sample. Suitable solvent dyes may include mono-azo dyes such as solvent yellow 124, bis-azo dyes such as solvent red 19, quinolines such as solvent yellow 33, medine dyes such as solvent yellow 93, xanthenes such as solvent green 4, perylkmes such as solvent green 5 and anthraquinone based dyes such as solvent blue 35. AppEcation of an ultraviolet W source or sufficiently Wight visible Wht source with a UV component to a solution containing both the dye and the photochromic compound results in a change in hue of the solution This change in hue on irradiation would indicate the presence of the photochrome as conventional dyestuns do not exhibait such a property.
Likewise, the photochromic compounds may be used in combination with, or added as a mixture with, colourless marker chemicals which are frequently used in fuels and that require alkaline conditions for the formation of colour. Thus, they may be used in conjunction with, for example, quinizarin, coumarin and compounds described in WO 96/32462 where the colour formed is in the extracted alkaline layer.
Such photochromic compounds may also be used in combination with, or added as a mixture with, colourless marker chemicals that require an acid for the formation of colour.
Thus, the photochromic compounds may be used in coton with, basic azo dyes, for example solvent yellow 124 or compounds described in WO 95/17483, winch require acidic conditions for the formation of colour, provided that the photochromicity is demonstrated prior to testing with the acid.
Claims (31)
1. A method of marking liquids comprising the steps of adding a photochromic
compound to the liquid and exposing the liquid to ultraviolet light to increase the
visibility of the photochromic compound whereby the colour or intensity of the
compound after exposure to ultraviolet light acts as an identification marker for
the liquid.
2. A method as claimed in claim 1, wherein the photochromic compound is added to
the liquid to be marked at a concentration that imparts no visible colour to the
liquid.
3. A method as claimed in claim 1 or 2, wherein the photochromic compound
becomes visible upon exposure to ultraviolet light.
4. A method as claimed in claim 1,2 or 3, wherein the liquid is cooled to a low
temperature during exposure to ultraviolet light to produce maximum intensity of
colour.
5. A method as claimed in claim 4, wherein a temperature in the range of-100 C to 45 C is provided during exposure to ultraviolet light.
6. A method as claimed in claim 5, wherein a temperature in the range of-80 C to 25 C is provided during exposure to ultraviolet light.
7. A method as claimed in any one of the preceding claims, wherein the absorbance
of the photochromic compound on exposure to ultraviolet light, under the
appropriate temperature conditions, is greater than 0.1.
8. A method as claimed in claim 7, wherein the absorbance of the photochromic
compound is greater than 0. 6.
9. A method as claimed in claim 8, wherein the absorbance of the photochromic
compound is 0.8 to 1.
10. A method as claimed in any one of the preceding claims, wherein the marked
liquid is illuminated at a constant distance for a constant length of time at a
specified temperature to ensure reproducibility of the colour formation thereby
ensuring the correct identification of the liquid from the detected marker.
11. A method as claimed in any one of the preceding claims, wherein a sample of the
liquid to be identified is stored in a light free environment prior to exposure.
12. A method as claimed in any one of claims 1 to 10, wherein a sample of the liquid
to be identifie is heated in a sealed vial prior to illumination.
13. A method as claimed in any one of the preceding claims, further comprising the
step of reversing the increased visibility of the compound by removal of the
ultraviolet light.
14. A method as claimed in any one of the preceding claims, wherein the
photochromic compound is provided as a liquid concentrate of between 1 % to
10% of the marker in an organic solvent.
15. A method as claimed in claim 14, wherein the organic solvent is an alky ! benzene,
alkylnaphthalene or a proprietary blend of such compounds.
16. A method as claimed in claim 14 or claim 15, wherein a polar organic solvent is
used to increase the solubility of the marker compound in the concentrate.
A method as claimed in claim 14, wherein the solvent is a mixture of aromatic
and aprotic solvents.
18. A method as claimed in any one of the preceding claims, wherein the final
concentration of the marker in the liquid to be marked is between 1 ppm and
30ppm (w/vol).
19. A method as claimed in any one of the preceding claims, wherein the
photochromic compounds are used in conjunction with solvent dyes.
20. A method as claimed in any one of claims 1 to 18, wherein the photochromic
compounds are used in conjunction with colourless marker chemicals which
require alkaline or acidic conditions for formation of colour in an extracted
aqueous layer.
21. A method as claimed in any one of the preceding claims for use in marking fuel
22. The use of a compound for marking liquids wherein the compound is a spiro
oxazine.
23. The use of a compound as claimed in claim 22, wherein the spiro-oxazine is a
spiro (indolino) oxazine.
24. The use of a compound as claimed in claim 23, wherein the spiro-oxazine has tl
general formula : wherein :-
Ri is a hydrogen atom, a Iinear or branched alkyl, alkenyl, allynyl, phenyl, phenylalkyl, mono-, di-or tri- substituted phenyl, alkoxy or alkoxyalkyl, carbocyclic, alkylcarbocyclic, heterocyclic or alkylheterocyclic ring and may be fused to ring A;
R2 and R3 independently represent a hydrogen atom, a linear or branched alkyl alkenyl, carbocyclic or heterocyclic ring, phenyl, phenylalkyl such as benzyl, mono-, di-or ui-substituted phenyl and may together represent an alicyclic ring which may be further substhed with alkyl, aryl or heteroaryl groups and may include spiro carbons, norbomane andadamantane ; R4 is a hydrogen atom, an alkyl, alkoxy, aryl, heteroaryl or amino group ;
Rs is hydrogen or an amine functionality of general formula-NRR", wherein each of R'and R"independently represents a hydrogen atom or an alkyl, cycloalkyl or phenyl group or a substituted derivative thereof or an amine functionality which is a cycloheteroalkyl ring or a substituted cycloheteroalkyl ring whose ring includes one or more heteroatoms, or a group of trmula-R, 4R,-SR,-COR or COOR wherein R represents a hydrogen atom, alkyl, aryl, or heteroaryl, or-Z, CH2Z,-CHZ2 or-CZ3 wherein Z represents a halogen or nitro, cyano or thiocyano group ; or with R6 forms a cyclo-group selected from a heterocyclic, optionally substituted, 5-membered ring or a six-membered carbocyclic or beterocyclic moiety, the hetero-atom being selected from O, S, Se, NH or NRr where RT represents an alkyl group and may be further substituted with alkyl, aryl, heteroaryl carbocyclic or heterocyclic rings fused thereto and optional substituents being selected from alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen, azo, imino, amide, ester, cyano, trifluoromethyl, nitro or dialkylamino groups; or is selected from alkenyl, alkynyl, imino, azo, amino, carboxy ester, amide, cyano or trifluoromethyl ;
R6 is hydrogen or is a group as defined above for R5 ;
7 is a group as defined above for Rs or when Rs and R6 form a six-membered carbocyclic or heterocyclic moiety is a group selected from aryl, heteroaryl, heterocyclic, alkenyl, alkenylaryl, cycloalkenyl, cycloalkenylaryl, alkynyl, alkynylaryl, nninoaryl, and azoaryl with a linkage to at least one amino or alkoxy group; or when 5 and R6 form a cyclo-group as defined above is a group of the formula NR*R in which Rx and Ry may be the same or different and may include alkyl, carbocyclic, aryl or heterocyclic groups or may be part of a heterocyclic ring together with the nitrogen atom to which they are attached, this ring possessing one or more heteroatoms and which in turn may bare further alkyl fused aryl or heteroaryl groups; Re is a group as defined above for R5 or when R5 and R6 form a cyclo-group as defined above is a hydrogen atom or a substituent selected from alkyL alkoxy, aryl, aryloxy, heteroaryl, halogen, azo, imino, amide, ester, cyano, trifluoromethyl, nitro or dialkylamino groups or when R5 and R6 form a six-membered carbocyclic or heterocyclic moiety is a group selected from hydrogen, allyl, alkoxy, alkenyl, alkynyl, imino, azo, amino, carboxy ester, amide, cyano, halogen, trifluoromethyl, nitro, aryl or heteroaryl ;
and Ring"A"is a carbocyclic, heterocyclic or benzene ring which is substituted by a group (R9) D n being an integer between 0 and 4, R9 being a hydrogen atom or an amine functionality of general formula-NRR"as defined above with reference to R5, a group of formula-R,-OR,-SR,-COR or COOR wherein R represents a hydrogen atom, alkyl aryl, or heteroaryl, or-Z, CH2Z,-CHZ2 or-CZ3 wherein Z represents a halogen or nitro, cyano or thiocyano group, or an alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen, azo, imino, amide, ester, cyano, trifluoromethyl, nitro or dialkylamino grotp or Ring A may optionally have a carbocyclic or heterocyclic ring fused to iL
25. The use of a compomjd as claimed in claim 24 of the formula :
26. The use of a compound for marking liquids wherein the compound is a
heterocyclochromeme.
27. The use of a compound as claimed in claim 26, wherein the compound is a
benzopyran.
28. The use of a compound as claimed in claim 27 of the general formulawherein :
R10 may represent a five membered heterocyclic group containing one or more heteroatoms and fused either to the f-face or the g-face of the benzo moiety of the benzopyran such that the heteroatom in the heterocycle is fused directly to a carbon atom on the benzo moiety and optionally the fused heterocyclic group can have in turn a further carbocyclic group, heterocyclic group of a group of formula R13 as defined belovv ; Rm and R12 may independently represent a carbocyclic or heterocyclic group or taken with the imervening carbon may be part of a carbocyclic or heterocyclic ring system; R13 may represent a hydrogen atom or a substituent selected from alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen, substituted or unsubstituted amino, azo, imino, amide, ester, cyano, trifluoromethyl or nitro groups.
29. The use of a compound as claimed in claim 26, wherein the compound is a naphthopyran.
30. The use of a compound as claimed in claim 29 having the general formula :wherein :
e represents a group of formula -NR15R16 wherein each of R15 and R16 independently represent alkyL carbocyclic or heterocyclic groups, or when taken with the intervening nitrogen atom to which they are attached a heterocyclic ring having one or more heteroatoms and which may optionally carry at least one substituent selected from alkyl, aryl or heteroaryl groups; R17 and R18 independently represent alkyl, alkenyl, carbocyclic or heterocyclic groups which may bear further alkyl, carbocyclic or heterocyclic groups as substments, or when taken together with the intervening carbon atom to which they are attached a carbocyclic or heterocyclic ring; R19 represents a hydrogen atom, alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen, a group of formula R14 as descr'bed above, azo, imnno, amide, carboxylate, ester, cyano, trifluoromethyl or nitro, or additionally Rl9 may represent a carbocyclic or heterocyclic ring fused to ring C. R14 may alternatively or aryloxy group and R19 can additionally be an amino group.
31. The use of a compound as claimed in claim 30 of the formula :-
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9827179.4A GB9827179D0 (en) | 1998-12-10 | 1998-12-10 | Method for marking liquids and compounds for use in said method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9905117D0 GB9905117D0 (en) | 1999-04-28 |
| GB2344599A true GB2344599A (en) | 2000-06-14 |
Family
ID=10843969
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GBGB9827179.4A Ceased GB9827179D0 (en) | 1998-12-10 | 1998-12-10 | Method for marking liquids and compounds for use in said method |
| GB9905117A Withdrawn GB2344599A (en) | 1998-12-10 | 1999-03-06 | Method for marking liquids and compounds for use in said method |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GBGB9827179.4A Ceased GB9827179D0 (en) | 1998-12-10 | 1998-12-10 | Method for marking liquids and compounds for use in said method |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB9827179D0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022161960A1 (en) | 2021-01-29 | 2022-08-04 | Basf Se | A method of marking fuels |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527709A (en) * | 1969-01-14 | 1970-09-08 | James R Alburger | Fluorescent tracer process and compositions |
| US4278444A (en) * | 1980-04-22 | 1981-07-14 | Mobil Oil Corporation | Liquid hydrocarbons containing a fluorescent compound |
| US5279967A (en) * | 1992-01-24 | 1994-01-18 | Nalco Chemical Company | Fluorescent labeling of hydrocarbons for source identification |
| GB2280265A (en) * | 1993-07-21 | 1995-01-25 | Molecular Light Technology Lim | Monitoring bulk liquids for presence of an additive |
| US5525516A (en) * | 1994-09-30 | 1996-06-11 | Eastman Chemical Company | Method for tagging petroleum products |
| US5804447A (en) * | 1992-07-23 | 1998-09-08 | Basf Aktiengesellschaft | Use of compounds which absorb and/or fluoresce in the IR region as markers for liquids |
-
1998
- 1998-12-10 GB GBGB9827179.4A patent/GB9827179D0/en not_active Ceased
-
1999
- 1999-03-06 GB GB9905117A patent/GB2344599A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527709A (en) * | 1969-01-14 | 1970-09-08 | James R Alburger | Fluorescent tracer process and compositions |
| US4278444A (en) * | 1980-04-22 | 1981-07-14 | Mobil Oil Corporation | Liquid hydrocarbons containing a fluorescent compound |
| US5279967A (en) * | 1992-01-24 | 1994-01-18 | Nalco Chemical Company | Fluorescent labeling of hydrocarbons for source identification |
| US5804447A (en) * | 1992-07-23 | 1998-09-08 | Basf Aktiengesellschaft | Use of compounds which absorb and/or fluoresce in the IR region as markers for liquids |
| GB2280265A (en) * | 1993-07-21 | 1995-01-25 | Molecular Light Technology Lim | Monitoring bulk liquids for presence of an additive |
| US5525516A (en) * | 1994-09-30 | 1996-06-11 | Eastman Chemical Company | Method for tagging petroleum products |
| US5525516B1 (en) * | 1994-09-30 | 1999-11-09 | Eastman Chem Co | Method for tagging petroleum products |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022161960A1 (en) | 2021-01-29 | 2022-08-04 | Basf Se | A method of marking fuels |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9827179D0 (en) | 1999-02-03 |
| GB9905117D0 (en) | 1999-04-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |