WO1999067346A1 - Use of amino azoic dyes as markers of oil distillation products - Google Patents

Use of amino azoic dyes as markers of oil distillation products Download PDF

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Publication number
WO1999067346A1
WO1999067346A1 PCT/EP1999/004354 EP9904354W WO9967346A1 WO 1999067346 A1 WO1999067346 A1 WO 1999067346A1 EP 9904354 W EP9904354 W EP 9904354W WO 9967346 A1 WO9967346 A1 WO 9967346A1
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Prior art keywords
use according
formula
markers
solution
hydrogen
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Application number
PCT/EP1999/004354
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French (fr)
Inventor
Enrico Traverso
Original Assignee
Societa' Italiana Additivi Per Carburanti S.R.L.
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Publication date
Priority claimed from IT98MI001454 external-priority patent/IT1301804B1/en
Priority claimed from IT98MI001881 external-priority patent/IT1302017B1/en
Priority to EP99932715A priority Critical patent/EP1097188B1/en
Priority to US09/736,022 priority patent/US6339145B1/en
Priority to DE69901258T priority patent/DE69901258D1/en
Priority to AT99932715T priority patent/ATE215982T1/en
Application filed by Societa' Italiana Additivi Per Carburanti S.R.L. filed Critical Societa' Italiana Additivi Per Carburanti S.R.L.
Priority to CA002335628A priority patent/CA2335628A1/en
Priority to JP2000555992A priority patent/JP2002518581A/en
Priority to AU49004/99A priority patent/AU4900499A/en
Priority to BR9911402-0A priority patent/BR9911402A/en
Priority to KR1020007014371A priority patent/KR20010052979A/en
Publication of WO1999067346A1 publication Critical patent/WO1999067346A1/en

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/22Fuels; Explosives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/003Marking, e.g. coloration by addition of pigments
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00Monoazo dyes prepared by diazotising and coupling
    • C09B29/06Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08Amino benzenes
    • C09B29/0805Amino benzenes free of acid groups
    • C09B29/0807Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/0811Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
    • C09B29/0813Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by OH, O-C(=X)-R, O-C(=X)-X-R, O-R (X being O,S,NR; R being hydrocarbonyl)
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S534/00Organic compounds -- part of the class 532-570 series
    • Y10S534/02Azo compounds containing chains of eight or more carbon atoms not provided for elsewhere in this class

Definitions

  • the present invention relates to the use of aminic azo dyes and their solutions in organic solvents, as pH depending markers of petrols, gas oils and generally for oil distillation products .
  • Petrols and gas oils are often additioned with small amounts, from 5 to 40 ppm, of liquid compositions of markers, in order to identify the oil product origin or for fiscal reasons .
  • the markers in many cases are constituted by liquid compositions of azoic dyes in organic solvents, which generally dye the oil products in yellow.
  • the marker control and its identification are carried out by treating a small amount of the oil product, depending on the marker, with an hydrophilic solution of a base or of an acid, which optionally can contain an organic solvent miscible with water.
  • the marker under these conditions undergoes a pH depending reaction with colour change.
  • the extraction solutions assume more or less intense colorations, with a colour ranging from the red to the violet, to blue.
  • extractable in basic medium Mortrace ® SB and ST can be mentioned.
  • Sudan Marker ® 455 C.I. Solvent Yellow 124 -BASF
  • This latter marker has an high absorbance as defined below, but it has the drawback to be synthetized with an industrially very expensive process, which besides the diazo-copulation reaction requires also an additional process step consisting in the condensation reaction with a vinylether.
  • azoaminic markers extractable in acid medium for example those described in the patent application WO 95/17483, are known. Tests carried out by the Applicant have shown that the azoaminic markers in which the nitrogen substituents are aliphatic groups, in the acid solution have a low specific absorbance E 1% 1 cm , defined as the absorbance referred to a solution at 1% w/v concentration in a 1 cm cell. See the Examples .
  • the Applicant has unexpectedly and surprisingly found compounds to be used as markers of oil distillation product which overcome the above mentioned drawbacks.
  • R is linear or branched alkyl with a number of carbon atoms from 4 to 20;
  • R 2 and R 3 are independently H, CH 3 , C 2 H 5 , OCH 3 ,
  • R and R are independently H , CH 3 , C 2 H 5 ;
  • X is H , OH ;
  • Y is hydrogen or the following poly-isopropoxy chain
  • n is comprised between 1 and 4; and of their concentrated compositions having a high dry titre in organic solvents, containing from 40 to 100% by weight of
  • R 1 is -C 12 H 25 aliphatic radical or sec. butyl, the R and R substituents are independently from each other hydrogen, CH 3 , 0CH 3 ;
  • R 4 is hydrogen and X is hydrogen or OH,
  • R 5 is hydrogen,
  • Y is H or the radical of formula la wherein n is comprised between 1 and 3
  • aromatic hydrocarbons usable as azodyes solvents are xylene, alkylnaphthalenes , the aromatic hydrocarbon mixture having from 10 to 11 carbon atoms known as Shellsol ® AB; examples of solvents having a polarity greater than that of the aromatic hydrocarbons and comprising in the molecule one or more functional groups containing oxygen are 2-butoxyethanol , butylcellosolve acetate and diacetonalcohol .
  • the compounds of formula (I) are extracted from the oil product by means of acid solutions of strong, inorganic and/or organic acids, having the following composition (% by volume): from 5 to 90% of an aqueous solution of a strong acid, having a molarity equal to or higher than 0.5 M; from 95 to 10% of an hydrosoluble organic solvent.
  • the extraction phase if necessary can be repeated more times in order to completely extract the marker.
  • strong acids are halohalide acids, sulphuric acid, nitric acid, phosphoric acid; mono-, di-, tri-chloroacetic acid.
  • hydrosoluble organic solvents examples include alcohols such as methylic, ethylic, isopropylic alcohol; polyols as mono-, di-, polyethylenglycols , glycerine; ether-alcohols such as methoxy- ethoxy- , butoxy-ethanol ; dimethylformamide, di- methylsulphoxide .
  • an additive can be added, soluble in the acid mixed aqueous/organic phase used for the extraction, to decrease the background coloration of the extraction solution.
  • a salt in amount from 5 to 20% w/v can be used.
  • Examples are KC1 , CaCl 2 , ZnCl 2 , ZnS0 4 , A1C1 3 .
  • Table 1 in the Table the marker concentrations in the concentrated liquid compositions are 0.1 mole/70 g of composition, calculated by supposing a synthesis yield of 100%) .
  • the marker concentrated compositions have been added to the oil product (gas oil for autotraction, see the Examples) to give marker concentrations in the range 0.5-10 ppm.
  • the extraction has been carried out as described above.
  • the extraction solution coloration moves towards ⁇ max values lower than the previous ones, up to about 480 nm, towards the red and orange since the background colour is present .
  • the peak corresponding to the maximum absorption wave length results clearly identifiable also under these conditions.
  • the Applicant thinks that the greater specific absorbance of the markers of the present invention is due to the association between the hydroxyl group which are in the nitrogen substituent aliphatic groups of these compounds and the organic solvent in the extraction solution.
  • the markers of the present invention have in the extraction solvent an high absorbance comparable, the concentration being equal, with that of Sudan Marker ® 455.
  • the present invention markers are obtainable with a simpler process, as described hereinunder.
  • the present invention markers are added to the oil distillation products in amounts from 0.5 to 50 ppm .
  • the present invention markers can be used in admixture
  • R is linear or branched alkyl with a number of
  • R 2 , R , R and R , X and Y are as defined in formula
  • the compounds of formula (I) are synthetized by starting from primary aromatic amines mono-alkyl substituted in the ring and by tertiary aromatic amines N,N disubstituted with alkylic chains containing at least an hydroxyl group.
  • the aromatic aminic copulating agent for obtaining the compounds of formula (I) when Y is the radical of formula (IA) is prepared by reacting the aromatic amine having one branched alkyl group of formula: -CH 2 -CH (R 5 ) -OH with the requested number of moles of 1 , 2-propylene oxide, at a temperature comprised between 140-170°C, in the presence of a base catalyst, such as KOH, CH 3 ONa, etc.) .
  • the raw materials are easily available on the market. Furthermore, the hydroxylated tertiary aromatic amines used in the present synthesis are not classified as toxic.
  • the process to obtain the markers, and which allows to obtain contemporaneously also the respective concentrated compositions having a high dry titre in organic solvents comprises the following steps:
  • step 3 the solvent can be evaporated at reduced pressure and the product is obtained.
  • step 2) after isopropyl alcohol recovery and elimination of the aqueous phase by siphoning, the organic phase is concentrated under vacuum at 115-120°C and clarified by filtering on sintered filter having an average porosity (G3 porosity) . If the final solution is too viscous, the clarification by filtering is carried out before the concentration phase.
  • G3 porosity average porosity
  • the aromatic amine diazotization is carried out by adding during one hour, under stirring, by dropping funnel, 73 ml of a 20% NaN0 2 w/v aqueous solution.
  • the reaction mixture temperature is maintained at 0°C with minced ice portions. At the end it is left under stirring for further 20 minutes.
  • the diazonium salt solution has a final volume of 350 ml.
  • the hydroalcoholic solution containing 0.21 moles of the diazonium salt of the dodecylaniline previously prepared is added in one hour and 30 minutes, by dropping funnel.
  • 160 ml of a 20% Na 2 C0 3 (w/v) solution are contemporaneously added in a total time of 2 hours and 30 minutes.
  • the pH is in the range 2-5.
  • the reaction mixture is maintained for other 4 hours under stirring, letting the temperature reach the room one.
  • the dropping funnels are taken away and substituted with a vigreux column connected to a claisen condenser.
  • the azeotrope water/isopropylic alcohol is distilled.
  • the compound is synthetized according to the method described in Example 1, using g 54.8 of dodecylaniline (0.21 moles) as diazotable base.
  • Example 2 The same procedure described in Example 1 is followed till to the filtration on sintered filter of the organic phase. After filtering, the phase is diluted with a Shellsol ® AB solvent portion used to wash the filter, obtaining 180 g total of solution.
  • Example 2 The process described in Example 2 is followed. Diazoti- zation is carried out on the same base; the copulating agent
  • the final organic solution in Shellsol ® AB has a weight of 140 g, the dye concentration is about 62%.
  • the preparation is made as described in Example 1. In the synthesis is used a quantity of the copulating agent prepared in ex. 13 of g. 61.4 (0.2 moles) . g 140 of a very viscous solution of the dye in Shellsol ® AB are obtained. Dry content : 83%.
  • Extractability test in aqueous acid of the dye of ex. 4 (dye IB) By performing the same procedure as in preceding example 15, it is observed that the dye is completely extracted by the acid solution.

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Abstract

Amino azoic dyes having general formula (I) wherein: R1 is linear or branched alkyl having from 4 to 20 carbon atoms; R?2 and R3¿ are independently H, CH¿3?, C2H5, OCH3, OC2H5; R?4 and R5¿ are independently H, CH¿3?, C2H5; X IS H, OH; Y is hydrogen or poly-isopropoxy chain (IA) wherein n is comprised between 1 and 4; they are used as markers of oil distillation product.

Description

USE OF AMINO AZOIC DYES AS MARKERS OF OIL DISTILLATION PRODUCTS
* * * * *
The present invention relates to the use of aminic azo dyes and their solutions in organic solvents, as pH depending markers of petrols, gas oils and generally for oil distillation products .
Petrols and gas oils are often additioned with small amounts, from 5 to 40 ppm, of liquid compositions of markers, in order to identify the oil product origin or for fiscal reasons .
The markers in many cases are constituted by liquid compositions of azoic dyes in organic solvents, which generally dye the oil products in yellow.
It is known that the marker control and its identification are carried out by treating a small amount of the oil product, depending on the marker, with an hydrophilic solution of a base or of an acid, which optionally can contain an organic solvent miscible with water.
The marker under these conditions undergoes a pH depending reaction with colour change. The extraction solutions assume more or less intense colorations, with a colour ranging from the red to the violet, to blue. Among the commercial markers extractable in basic medium Mortrace® SB and ST (Morton) can be mentioned. Among those extractable in acid ambient, Sudan Marker® 455 (C.I. Solvent Yellow 124 -BASF) is known. This latter marker has an high absorbance as defined below, but it has the drawback to be synthetized with an industrially very expensive process, which besides the diazo-copulation reaction requires also an additional process step consisting in the condensation reaction with a vinylether.
Furthermore, other azoaminic markers extractable in acid medium, for example those described in the patent application WO 95/17483, are known. Tests carried out by the Applicant have shown that the azoaminic markers in which the nitrogen substituents are aliphatic groups, in the acid solution have a low specific absorbance E1% 1 cm, defined as the absorbance referred to a solution at 1% w/v concentration in a 1 cm cell. See the Examples .
The need was felt to have available markers which in the extraction acid solution have high specific absorbance E1* cm characteristics at the respective wave length of maximum absorption, and obtainable with a simplified process.
The Applicant has unexpectedly and surprisingly found compounds to be used as markers of oil distillation product which overcome the above mentioned drawbacks.
It is an object of the present invention the use as markers of oil distillation product of amino azoic dyes having the general formula
Figure imgf000005_0001
wherein :
R is linear or branched alkyl with a number of carbon atoms from 4 to 20;
R2 and R3 are independently H, CH3 , C2H5, OCH3 ,
OC2H5 ;
R and R are independently H , CH3 , C2H5 ;
X is H , OH ;
Y is hydrogen or the following poly-isopropoxy chain
: CH 2-CH-0)n-H (IA)
CH, wherein n is comprised between 1 and 4; and of their concentrated compositions having a high dry titre in organic solvents, containing from 40 to 100% by weight of
said azodyestuffs .
For the use according to the present invention preferably in the formula (I) compounds R1 is -C12H25 aliphatic radical or sec. butyl, the R and R substituents are independently from each other hydrogen, CH3 , 0CH3 ; R4 is hydrogen and X is hydrogen or OH, R5 is hydrogen, Y is H or the radical of formula la wherein n is comprised between 1 and 3
The organic solvent of the compositions having an high dry titre is selected from aromatic hydrocarbons having a number of carbon atoms from 7 to 15, optionally containing one or more C-^^ aliphatic chains, and mixtures thereof, or solvents having a greater polarity than that of the above mentioned hydrocarbons, comprising in their molecule one or more functional groups containing oxygen, in which oxygen is bound by covalent bonds, such as for example ethers, alcohols, and/or with double bond =0 such as for example esters, ketones , etc .
Examples of aromatic hydrocarbons usable as azodyes solvents are xylene, alkylnaphthalenes , the aromatic hydrocarbon mixture having from 10 to 11 carbon atoms known as Shellsol® AB; examples of solvents having a polarity greater than that of the aromatic hydrocarbons and comprising in the molecule one or more functional groups containing oxygen are 2-butoxyethanol , butylcellosolve acetate and diacetonalcohol .
According to the object of the present invention the compounds of formula (I) are extracted from the oil product by means of acid solutions of strong, inorganic and/or organic acids, having the following composition (% by volume): from 5 to 90% of an aqueous solution of a strong acid, having a molarity equal to or higher than 0.5 M; from 95 to 10% of an hydrosoluble organic solvent.
The extraction phase if necessary can be repeated more times in order to completely extract the marker. Examples of strong acids are halohalide acids, sulphuric acid, nitric acid, phosphoric acid; mono-, di-, tri-chloroacetic acid.
Examples of hydrosoluble organic solvents are alcohols such as methylic, ethylic, isopropylic alcohol; polyols as mono-, di-, polyethylenglycols , glycerine; ether-alcohols such as methoxy- ethoxy- , butoxy-ethanol ; dimethylformamide, di- methylsulphoxide .
Optionally an additive can be added, soluble in the acid mixed aqueous/organic phase used for the extraction, to decrease the background coloration of the extraction solution. For example a salt in amount from 5 to 20% w/v can be used. Examples are KC1 , CaCl2, ZnCl2, ZnS04 , A1C13.
In the extraction tests carried out by the Applicant to show the advantages obtainable with the use of the present invention markers, in a first series of tests, solutions obtained by diluting in isooctane the marker concentrated liquid compositions up to concentration 5 - 20 ppm, have been used. These yellow-coloured solutions have a wave length at the absorption peak λmax in the range 395 - 410 nm. The extraction acid solutions have a magenta red colour with λmax in the range 530 - 545 nm. The tests reported in the examples show that the invention markers in the extraction acid solutions have a very high specific absorbance E1 's 1 cm, the concentration of the azoic compound being equal, in particular higher than 50%, in comparison with the above mentioned azoaminic markers.
For example the specific absorbance E1 1 cm of the N- ethyl-N- (2-hydroxyethyl) -4- [ (dodecylphenyl ) -azo] -m-toluidine compound, in concentrated liquid composition at concentration 0.1 moles/70 g, is 775 (λmaχ = 538 nm) in the acid hydroal- coholic solution used for the extraction (HC1 lON/ethanol 50/50 v/v) , while the one of the composition containing N,N- diethyl-4- [ (dodecylphenyl) -azo] -m-toluidine is 424 (λmax = 535 nm) . See Table 1 (in the Table the marker concentrations in the concentrated liquid compositions are 0.1 mole/70 g of composition, calculated by supposing a synthesis yield of 100%) .
In a second series of tests the marker concentrated compositions have been added to the oil product (gas oil for autotraction, see the Examples) to give marker concentrations in the range 0.5-10 ppm. The extraction has been carried out as described above. The extraction solution coloration moves towards λmax values lower than the previous ones, up to about 480 nm, towards the red and orange since the background colour is present . However the peak corresponding to the maximum absorption wave length results clearly identifiable also under these conditions.
Without to be bound to any theory, the Applicant thinks that the greater specific absorbance of the markers of the present invention is due to the association between the hydroxyl group which are in the nitrogen substituent aliphatic groups of these compounds and the organic solvent in the extraction solution.
The markers of the present invention have in the extraction solvent an high absorbance comparable, the concentration being equal, with that of Sudan Marker® 455. However the present invention markers are obtainable with a simpler process, as described hereinunder.
It has been found by the Applicant that formula (I) compounds wherein R1 = C4H9 are extractable also with aqueous acids (ex. HCl 5N) . However the solution coloration intensity is lower than that obtained in an aqueous solution in admixture with an organic water-soluble solvent.
The preferred markers are those wherein R1 of formula (I) is a linear or branched alkyl having from 6 to 20 carbon atoms, said compounds having a specific absorbance E1's 1 cm in the mixed aqueous/organic extraction solution higher than those markers wherein R1= C4 alkyl . See Table I .
The present invention markers, or the corresponding compositions in organic solvents having a high dry titre, are added to the oil distillation products in amounts from 0.5 to 50 ppm .
The present invention markers can be used in admixture
with other markers and/or dyes used in this field, which are
selected among those which do not interfere in the described
extraction process.
It is a further object of the present invention compounds
of formula (IX) :
Figure imgf000010_0001
wherein :
R is linear or branched alkyl with a number of
carbon atoms from 6 to 20;
R2 , R , R and R , X and Y are as defined in formula
(I) .
Said dyes, besides having the advantageous
spectrophotometric properties above said over those of the
compounds of the same formula wherein R1= C4 alkyl, are not
extracted with aqueous acids. This properties make it possible
their use in combination with a blue dye as additives to make
petrol green-coloured under the provisions of the Italian
Ministerial Decree 6.3.97, that states that said dyes must
not be extractable with aqueous acids. The compounds of formula (I) are synthetized by starting from primary aromatic amines mono-alkyl substituted in the ring and by tertiary aromatic amines N,N disubstituted with alkylic chains containing at least an hydroxyl group.
The aromatic aminic copulating agent for obtaining the compounds of formula (I) when Y is the radical of formula (IA) , is prepared by reacting the aromatic amine having one branched alkyl group of formula: -CH2-CH (R5) -OH with the requested number of moles of 1 , 2-propylene oxide, at a temperature comprised between 140-170°C, in the presence of a base catalyst, such as KOH, CH3ONa, etc.) .
The raw materials are easily available on the market. Furthermore, the hydroxylated tertiary aromatic amines used in the present synthesis are not classified as toxic.
The process to obtain the markers, and which allows to obtain contemporaneously also the respective concentrated compositions having a high dry titre in organic solvents, comprises the following steps:
1) diazotization, in hydroalcoholic solution of isopropyl alcohol, with nitrous acid of the primary aromatic amine having the Rχ group and obtainment of the corresponding diazonium salt;
2) diazonium salt copulation with the aromatic amine N,N disubstituted with alkyl chains containing at least one hydroxyl group, at 0°C and at pH between 2 and 5 buffered with a sodium carbonate or a sodium acetate solution, in the presence of an aromatic solvent as defined, from which the formed product is extracted; 3) Recovery of the solution in the organic solvent having a high dry titre ready to be use.
Alternatively to step 3) the solvent can be evaporated at reduced pressure and the product is obtained.
At the end of step 2) , after isopropyl alcohol recovery and elimination of the aqueous phase by siphoning, the organic phase is concentrated under vacuum at 115-120°C and clarified by filtering on sintered filter having an average porosity (G3 porosity) . If the final solution is too viscous, the clarification by filtering is carried out before the concentration phase.
Examples illustrating the invention are reported hereinafter, which are not to be considered limitative of the scope of the same . EXAMPLE 1
Synthesis of N-ethyl-N- (2 -hydroxyethyl) -4- [ (dodecylphenyl) - azo] -m-toluidine (compound C)
Figure imgf000012_0001
In a 1 1 four-necked flask, with stirrer and dropper, 54.8 g (0.21 moles) of dodecylaniline CAS [68411-48-3], 80 ml of isopropyl alcohol, 63 ml of HCl 10 N and minced ice are introduced.
The aromatic amine diazotization is carried out by adding during one hour, under stirring, by dropping funnel, 73 ml of a 20% NaN02 w/v aqueous solution. The reaction mixture temperature is maintained at 0°C with minced ice portions. At the end it is left under stirring for further 20 minutes. The diazonium salt solution has a final volume of 350 ml.
In a 1 litre flask with stirrer, 2 dropping funnels, 35.8 g (0.20 moles) of N-ethyl-N- (2-hydroethyl) -m-toluidine, 100ml of water, 20 ml of HCl 10 N and 100 ml of Shellsol® AB are introduced. The solution is cooled at 0°C by mixing with minced ice portions .
To this mixture at the temperature of 0°C under stirring, the hydroalcoholic solution containing 0.21 moles of the diazonium salt of the dodecylaniline previously prepared, is added in one hour and 30 minutes, by dropping funnel. By means of the other dropping funnel 160 ml of a 20% Na2C03 (w/v) solution are contemporaneously added in a total time of 2 hours and 30 minutes. The pH is in the range 2-5.
The reaction mixture is maintained for other 4 hours under stirring, letting the temperature reach the room one. At the end the dropping funnels are taken away and substituted with a vigreux column connected to a claisen condenser. The azeotrope water/isopropylic alcohol is distilled.
Stirring is stopped. The phases are quickly separated and the aqueous phase is siphoned. The organic phase is recovered which is dehydrated by heating to 115°C in nitrogen flow, under stirring. The solution is successively clarified by filtering on sintered filter (G3), then concentrated by heating at 115°C at the residual pressure of 30 mmHg .
140 g of a dye solution in Shellsol® AB are thus obtained. The dye solution has a concentration of about 66% by weight . EXAMPLE la
Extraction test of the dye C concentrated liquid composition diluted with isooctane.
In a 200 ml separatory funnel are introduced: 50 ml of isooctane containing 22.90 ppm w/v of liquid composition of product C directly obtained from the synthesis and having a calculated concentration of 0.1 mole/70 g, assuming a quantitative reaction yield (100%) . 50 ml of extracting solution, obtained by mixing 50 volumes of HCl 10 N with 50 volumes of anhydrous ethanol . The mass is strongly stirred for 30 seconds. The funnel is let stay. Two layers are quickly separated. The lower acid hydroalcoholic layer intensely colours into magenta red.
The E1% 1 cm and λmax values in isooctane and in the extraction solution are reported in Table I .
EXAMPLE 2
Synthesis of N , N-bis ( 2 -hydroxyethyl ) -4 - [ (dodecylphenyl ) zo] -m- toluidine ( compound D )
Figure imgf000015_0001
The compound is synthetized according to the method described in Example 1, using g 54.8 of dodecylaniline (0.21 moles) as diazotable base.
In a 1 litre flask with stirrer, 2 dropping funnels, 39 g (0.20 moles) of N, N-bis (2-hydroxyethyl) m.toluidine, 100 ml of water and 20 ml of HCl 10 N are introduced, stirring until complete dissolution. 100 ml of Shellsol® AB are subsequently added. The solution is cooled at 0°C by mixing with minced ice .
The same procedure described in Example 1 is followed till to the filtration on sintered filter of the organic phase. After filtering, the phase is diluted with a Shellsol® AB solvent portion used to wash the filter, obtaining 180 g total of solution.
The solvent is completely removed by evaporation up to 120-125°C and residual pressure of 30 mm Hg, obtaining a residue of tarry consistence weighing 95 g, which is treated with 45 g of diacetonalcohol to give a solution (g 140) having a concentration of about 65%. EXAMPLE 2a
Extraction test of the dye D concentrated liquid composition diluted with isooctane.
One proceeds as described in Example la.
The corresponding E1'ϊ 1 cm and λmaχ values in isooctane and in the extraction solution are reported in Table I . EXAMPLE 3
Synthesis of N,N-bis (2-hydroxyethyl) -4- f (dodecylphenyl) azo] -
aniline (compound B)
Figure imgf000016_0001
CH2—CH2 OH
The process described in Example 2 is followed. Diazoti- zation is carried out on the same base; the copulating agent
is N,N-bis (2-hydroxyethyl) aniline.
The final organic solution in Shellsol® AB has a weight of 140 g, the dye concentration is about 62%.
EXAMPLE 3a
Extraction test of the dye B concentrated liquid composition diluted with isooctane. One proceeds as described in Example la.
The corresponding E1% x cm and λmax values in isooctane and in the extraction solution are reported in Table I . EXAMPLE 4 Synthesis of N-e hyl-N- (2-hvdroxyethyl) -4- \ (p-sec .butvlphenvl-
) azo] -m-toluidine (compound IB)
Figure imgf000017_0001
By operating with the same procedures of Example 1 and by using 31.3 g of p-sec .butylaniline (0.21 moles) as diazotiza- ble base and 35.8 g (0.2 moles) of N-ethyl-N- (2-hydroxyethyl) - m-toluidine as copulating base, 140 g of liquid composition based on the azoic dye are prepared. The dry product titre is about 50%. EXAMPLE 4a
Extraction test of dye IB concentrated liquid composition diluted with isooctane.
One proceeds as described in Example la.
The corresponding E1% 1 cm and λmax values in isooctane and in the extraction solution are reported in Table I . EXAMPLE 5 (comparative)
Synthesis of N,N-diethyl-4- [ (p-sec .butylphenyl) -azo] -m-toluidine (compound IC)
Figure imgf000018_0001
By operating with the same procedures of Example 1 and by using 31.3 g of p-sec .butylaniline (0.21 moles) as diazotizable base and 32.6 g (0.2 moles) of N,N-diethyl-m-toluidine as copulating base, 140 g of liquid composition based on the azoic dye are prepared. The dry product titre is 48%. EXAMPLE 5a (comparative)
Extraction test of the dye IC concentrated liquid composition diluted with isooctane.
One proceeds as described in Example la.
The corresponding E1^ cm and λmax values in isooctane and in the extraction solution are reported in Table I . EXAMPLE 6 (comparative) Synthesis of N,N-diethyl-4- \ (dodecylphenyl) -azo] -m-toluidine
[compound IF)
Figure imgf000018_0002
By operating with the same procedures of Example 1 and by
using 54.8 g of dodecylaniline (0.21 moles) as diazotizable base and 32.6 g (0.2 moles) of N, -diethyl-m-toluidine (0.2 moles) as copulating base, 140 g of liquid composition based on the azoic dye are prepared having a dry titre of about 65%. EXAMPLE 6a (comparative)
Extraction test of the dye IF concentrated liquid composition diluted with isooctane.
One proceeds as described in Example la.
The corresponding E1^ cm and λmax values in isooctane and in the extraction solution are reported in Table I . EXTRACTION TESTS OF THE PRODUCT C MARKER (Ex. 1) FROM GAS OIL FOR AUTOTRACTION. EXAMPLE 7
In a 200 ml separatory funnel 50 ml of gas oil for autotraction charged with 10 ppm w/v of product C liquid composition (Ex. 1) having a concentration of 0.1 moles/70 g, and 50 ml of extraction acid solution, obtained by mixing 25 volumes of HCL 10 N, 20 volumes of water and 55 volumes of ethanol , are introduced.
The mass is strongly stirred for 30 seconds. The funnel is let stay. Two layers are quickly separated. The lower acid hydroalcoholic layer colours red. The absorption spectrum shows a marked and clear peak at λmaχ = 533 nm. EXAMPLE 8
In a 250 ml separatory funnel, 150 ml of gas oil for autotraction, charged with 1 ppm w/v of product C liquid composition and 40 ml of extraction acid solution of Example 7, are introduced.
From the mass, strongly stirred, a lower acid hydroalcoholic layer is clearly separated which colours red and which shows a spectrophotometric peak at λmax = 489 nm. EXAMPLE 9
In a 200 ml separatory funnel, 100 ml of gas oil for autotraction, charged with 5.25 ppm w/v of product C liquid composition, are treated and stirred with 3 subsequent 20 ml parts of extraction acid solution formed by 70 volumes of dimethylformamide and 30 volumes of HCL 10 N.
The three parts are collected as lower phase and mixed together to give a limpid, red-coloured solution which shows a spectrophotometric peak at λmax = 532 nm. EXAMPLE 10
In a 200 ml separatory funnel, 100 ml of gas oil for autotraction, charged with 0.5 ppm of product C liquid composition, are treated and stirred with 3 subsequent 10 ml parts of extraction acid solution of Example 9.
The three parts are collected as lower phase and mixed together to give a limpid, red-orange-coloured solution having a spectrophotometric peak at λmax = 484 nm. EXAMPLE 11
In a 200 ml separatory funnel, 100 ml of gas oil for autotraction, charged with 2 ppm w/v of product C liquid composition, are treated and stirred with 40 ml of extraction acid solution consisting of 90 volumes of ethylenglycol and 10 volumes of HCl 10 N.
The limpid and red-coloured extraction solution is separated. It shows an absorption peak at λmaχ = 495 nm. EXAMPLE 12
In a 200 ml separatory funnel, 100 ml of gas oil for autotraction, charged with 0.5 ppm w/v of product C liquid composition, are treated and stirred with 20 ml of acid solution of Example 11.
The limpid and red-orange-coloured extraction solution is separated. It shows an absorption peak at λmaχ = 485 nm. EXAMPLE 13
Preparation of the aminic copulating agent of formula (13A)
Figure imgf000021_0001
)n-H
wherein n = 2.2, mol . wt . = 307 (pure product) 358 g (2 moles) of N-ethyl-N (2-hydroxyethyl) -m-toluidine and 9 g of powdered CH30Na are charged into 1 liter autoclave equipped with a magnetic stirrer and a heating-cooling jacket with forced oil circulation. The vessel is closed and air is removed by repeated nitrogen washings. Then heating is applied to raise the temperature of the solution to 150 °C. In continuum are then charged, by means of a tubing dipped into the organic solution, g 232 (4 moles) of 1, 2-propylene oxide. The reaction is exotermic and the temperature in the organic solution is maintained between 150-160°C by circulating in the vessel jacket oil cooled at room temperature. The reaction lasts 3 hours. The maximun pressure inside the reactor is of 4 Kg/cm2.
The organic solution is then cooled to room temperature. Vacuum is applied in order to remove the gas. The liquid phase is afterwards distilled under vacuum, to eliminate residual N- ethyl-N (2 -hydroxyethyl) -m-toluidine : at a temperature comprised between 132 and 160°C (temperature of the vapor phase) are distilled 42 g of an oil having a nitrogen content of 7.45%. The product left in the vessel is a yellowish oil (g 543) having a nitrogen content of 4.56% corresponding to an average molecular weight of 307, freely soluble in diluted HCl. Said product is used as such in the synthesis of the compound of formula (I) described in following example 14. EXAMPLE 14
Synthesis of N-ethyl-N (2-polyisopropoxyethyl) -4- [ (dodecyl phenyl) azo] -m-toluidine (compound G)
Figure imgf000022_0001
n = 2.2, molecular weight = 579
The preparation is made as described in Example 1. In the synthesis is used a quantity of the copulating agent prepared in ex. 13 of g. 61.4 (0.2 moles) . g 140 of a very viscous solution of the dye in Shellsol® AB are obtained. Dry content : 83%.
Example 14a
Extraction of the concentrated liquid dye composition of example 14 with iso-octane
The same procedure as that described in ex. la is repeated. In table I are given the corresponding values of ^1cm anc^ λmax values in isooctane and in the extraction solution. Example 15
Extractability test in aqueous acid of the dye of ex. 1 (dye C)
An heptane solution at 20 ppm w/v concentration of dye C is prepared by diluting conformingly with said solvent the liquid high dry concentrated dye composition of ex. 1. 10 ml of the heptane solution is shaked in a separatory funnel with 50 ml of aqueous HCl 5N. After phase separation, it is observed that the hydrochloric acid phase remains colourless . Example 16 (comparative)
Extractability test in aqueous acid of the dye of ex. 4 (dye IB) By performing the same procedure as in preceding example 15, it is observed that the dye is completely extracted by the acid solution.
Note : in following Table I the marker concentrations in the concentrated organic solutions before diluting with isooctane, are of 0.1 mole/70 g of composition, calculated by assuming the theoretical synthesis yield of 100%.
TABLE I
Figure imgf000025_0001
TABLE II
Figure imgf000026_0001

Claims

1. Use as markers of oil distillation products of amino azoic dyes having the general formula
Figure imgf000027_0001
wherein:
R1 is linear or branched alkyl having from 4 to 20 carbon atoms ;
R2 and R3 are independently H, CH3 , C2H5, 0CH3 ,
OC2H5 ;
R4 and R5 are independently H , CH3 , C2H5 ;
X is H, OH ;
Y is hydrogen or the following poly-isopropoxy chain
- (CH?-CH-0)n-H (IA)
I CH3 wherein n is comprised between 1 and 4 ; and of their concentrated compositions having a high dry
titre in organic solvents, containing from 40 to 100% by
weight of said azodyes .
Use according to claim 1, wherein in the formula (I) compounds R1 is the -C12H25 aliphatic radical or sec- butyl, the R and R substituents are independently hydrogen, CH3 , OCH3 ; R is hydrogen and X is hydrogen or OH, R is hydrogen, Y is H or the radical of formula la wherein n is comprised between 1 and 3.
3. Use according to claims 1-2, wherein the organic solvent of the compositions having an high dry titre is selected from aromatic hydrocarbons having from 7 to 15 carbon atoms, optionally containing one or more C1-C4 aliphatic chains, and mixtures thereof, or solvents comprising in their molecule one or more functional groups containing oxygen, wherein oxygen is bound by simple covalent bonds and/or with double bond =0.
4. Use according to claim 3 wherein the organic solvent is selected from: xylene, alkylnaphthalenes , the aromatic hydrocarbon mixture having from 10 to 11 carbon atoms, 2- butoxyethanol , butylcellosolve acetate and diacetonalcohol .
5. Use according to claims 1-4, wherein the formula (I) compounds are extracted from the oil product by acid solutions of strong, inorganic and/or organic acids, having the following composition (the percentages are by volume %) : from 5 to 90% of an aqueous solution of a strong acid, having a molarity equal to or higher than 0.5 M; from 95 to 10% of an hydrosoluble organic solvent. Use according to claim 5 wherein the hydrosoluble organic solvent is selected from alcohols, polyols, ethers alcohols, dimethylformamide, dimethylsulphoxide . Use according to claims 5-6 wherein a salt is added in amount from 5 to 20% w/v.
Use according to claim 7 wherein the salt is selected from KC1, CaCl2, ZnCl2, ZnS04 , A1C13.
Use according to claims 1-8 wherein the markers, or their corresponding concentrated compositions in organic solvents, are added to oil distillation products in amounts ranging from 0.5 to 50 ppm. Compounds of formula (IX) :
R- R4
Figure imgf000029_0001
R is linear or branched alkyl with a number of carbon atoms from 6 to 20;
R , R3 , R4 and R , X and Y are as defined in formula (I) .
PCT/EP1999/004354 1998-06-25 1999-06-23 Use of amino azoic dyes as markers of oil distillation products WO1999067346A1 (en)

Priority Applications (9)

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KR1020007014371A KR20010052979A (en) 1998-06-25 1999-06-23 Use of amino azoic dyes as markers of oil distillation products
BR9911402-0A BR9911402A (en) 1998-06-25 1999-06-23 Use of amino azo dyes and compounds
US09/736,022 US6339145B1 (en) 1998-06-25 1999-06-23 Use of amino azoic dyes as markers of oil distillation products
DE69901258T DE69901258D1 (en) 1998-06-25 1999-06-23 USE OF AMINO-AZO DYES AS A MARKING AGENT FOR OIL DISTILLATES
AT99932715T ATE215982T1 (en) 1998-06-25 1999-06-23 USE OF AMINO-AZO DYES AS MARKERS FOR OIL DISTILLATES
EP99932715A EP1097188B1 (en) 1998-06-25 1999-06-23 Use of amino azoic dyes as markers of oil distillation products
CA002335628A CA2335628A1 (en) 1998-06-25 1999-06-23 Use of amino azoic dyes as markers of oil distillation products
JP2000555992A JP2002518581A (en) 1998-06-25 1999-06-23 Use of aminoazo dyes as markers for oil distillation substances
AU49004/99A AU4900499A (en) 1998-06-25 1999-06-23 Use of amino azoic dyes as markers of oil distillation products

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IT98MI001454 IT1301804B1 (en) 1998-06-25 1998-06-25 Markers for oil distillation products
IT98MI001881 IT1302017B1 (en) 1998-08-11 1998-08-11 Markers for oil distillation products
ITMI98A001881 1998-08-11

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EP1421146A1 (en) * 2001-08-28 2004-05-26 United Color Manufacturing, Inc. Molecular tags for organic solvent systems
CN102495166A (en) * 2011-12-07 2012-06-13 晨光生物科技集团股份有限公司 Method for detecting content of azo-dye in lubricating oil
GB2490791A (en) * 2011-05-11 2012-11-14 Johnson Matthey Plc Tracers and method of marking hydrocarbon liquids

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ITMI20042519A1 (en) 2004-12-27 2005-03-27 Enrico Traverso AROMATIC-ALIPHATIC AZODERIVATES PARTICULARLY AS MARKERS FOR PETROLEUM PRODUCTS THEIR PROCESS OF SYNTHESIS THEIR USE AND DERIVED COMPOSITIONS
CN110023413B (en) 2016-07-15 2022-05-17 联合色彩制造股份有限公司 Compositions and methods for labeling hydrocarbon compositions with non-mutagenic dyes

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1421146A1 (en) * 2001-08-28 2004-05-26 United Color Manufacturing, Inc. Molecular tags for organic solvent systems
JP2005502760A (en) * 2001-08-28 2005-01-27 ユナイテッド・カラー・マニュファクチャリング・インコーポレイテッド Organic solvent based molecular tag
EP1421146A4 (en) * 2001-08-28 2010-09-29 United Color Mfg Inc Molecular tags for organic solvent systems
GB2490791A (en) * 2011-05-11 2012-11-14 Johnson Matthey Plc Tracers and method of marking hydrocarbon liquids
WO2012153133A1 (en) 2011-05-11 2012-11-15 Johnson Matthey Public Limited Company Method of marking hydrocarbon liquids
GB2490791B (en) * 2011-05-11 2013-12-25 Johnson Matthey Plc Method of marking hydrocarbon liquids
US9625440B2 (en) 2011-05-11 2017-04-18 Johnson Matthey Public Limited Company Method of marking hydrocarbon liquids
CN102495166A (en) * 2011-12-07 2012-06-13 晨光生物科技集团股份有限公司 Method for detecting content of azo-dye in lubricating oil
CN102495166B (en) * 2011-12-07 2014-04-16 晨光生物科技集团股份有限公司 Method for detecting content of azo-dye in lubricating oil

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