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Title:
USE OF AMINO AZOIC DYES AS MARKERS OF OIL DISTILLATION PRODUCTS
Document Type and Number:
WIPO Patent Application WO/1999/067346
Kind Code:
A1
Abstract:
Amino azoic dyes having general formula (I) wherein: R?1¿ is linear or branched alkyl having from 4 to 20 carbon atoms; R?2¿ and R?3¿ are independently H, CH¿3?, C¿2?H¿5?, OCH¿3?, OC¿2?H¿5?; R?4¿ and R?5¿ are independently H, CH¿3?, C¿2?H¿5?; 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.

Inventors:
Traverso, Enrico (Via Monte Bianco, 22 Monza, I-20052, IT)
Application Number:
PCT/EP1999/004354
Publication Date:
December 29, 1999
Filing Date:
June 23, 1999
Export Citation:
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Assignee:
SOCIETA' ITALIANA ADDITIVI PER CARBURANTI S.R.L. (Piazza Duca d'Aosta, 41 Pescara, I-65100, IT)
Traverso, Enrico (Via Monte Bianco, 22 Monza, I-20052, IT)
International Classes:
C10L1/22; C09B29/08; C10L1/00; (IPC1-7): C10L1/00; C09B29/08
Domestic Patent References:
WO1995017483A11995-06-29
Foreign References:
GB2022120A1979-12-12
US4011209A1977-03-08
US4904765A1990-02-27
US5182372A1993-01-26
Other References:
DATABASE WPI Section Ch Week 199518, Derwent World Patents Index; Class A82, AN 1995-137363, XP002118776
Attorney, Agent or Firm:
Sama, Daniele (Sama Patents Via G.B. Morgagni, 2 Milano, I-20129, IT)
Download PDF:
Claims:
CLAIMS
1. Use as markers of oil distillation products of amino azoic dyes having the general formula wherein: R1 is linear or branched alkyl having from 4 to 20 carbon atoms; R2 and R3 are independently H, CH3, C2H5, OCH3, OC2H5 i R4 and R5 are independently H, CH3, C2H5; X is H, OH; Y is hydrogen or the following polyisopropoxy chain 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 100k by weight of said azodyes.
2. Use according to claim 1, wherein in the formula (I) compounds R1 is theC12H2s aliphatic radical or sec. butyl, the R2 and R3 substituents are independently hydrogen, CH3, OCH3; 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.
3. Use according to claims 12, 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 C1C4 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 diaceto nalcohol.
5. Use according to claims 14, 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 t): from 5 to 90k 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.
6. Use according to claim 5 wherein the hydrosoluble organic solvent is selected from alcohols, polyols, ethers alcohols, dimethylformamide, dimethylsulphoxide.
7. Use according to claims 56 wherein a salt is added in amount from 5 to 20% w/v.
8. Use according to claim 7 wherein the salt is selected from KC1, CaCl2, ZnCl2, ZnS04, AlCl3.
9. Use according to claims 18 wherein the markers, or their corresponding concentrated compositions in organic solvents, are added to oil distillation products in amo unts ranging from 0.5 to 50 ppm.
10. Compounds of formula (IX) : Ri is linear or branched alkyl with a number of carbon atoms from 6 to 20; R2, R3, R4 and R5, X and Y are as defined in formula (I).
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 com- positions 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 depend- ing 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 re- action 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 <BR> <BR> <BR> <BR> a low specific absorbance Ell 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 <BR> <BR> <BR> <BR> <BR> extraction acid solution have high specific absorbance E1tl cm characteristics at the respective wave length of maximum ab- sorption, 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 wherein: R1 is linear or branched alkyl with a number of carbon atoms from 4 to 20; -R2 and R3 are independently H, CH3, C2H5, OCH3, <BR> <BR> <BR> <BR> <BR> OC2H5;<BR> <BR> <BR> <BR> <BR> -R4 and R5 are independently H, CH3, C2H5; -X is H, OH; -Y is hydrogen or the following poly-isopropoxy chain 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-Cl2H25 aliphatic radical or sec. butyl, the R2 and R3 substituents are independently from each other hydrogen, CH3, OCH3; 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 num- ber of carbon atoms from 7 to 15, optionally containing one or more Cl-C4 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 hydro- carbon 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 900 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, ZnSO4, AlCl3.

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 Xmax in the range 395-410 nm. The <BR> <BR> extraction acid solutions have a magenta red colour with Xmax in the range 530-545 nm. The tests reported in the examples show that the invention markers in the extraction acid <BR> <BR> <BR> <BR> <BR> solutions have a very high specific absorbance E 116 1 cm, the concentration of the azoic compound being equal, in particular higher than 50%, in comparison with the above mentioned azoaminic markers. <BR> <BR> <BR> <BR> <BR> <P> For example the specific absorbance E1Wl 1 of the N-<BR> <BR> <BR> <BR> <BR> <BR> ethyl-N-(2-hydroxyethyl)-4-[(dodecylphenyl)-azo]-m-toluidine compound, in concentrated liquid composition at concentration <BR> <BR> <BR> <BR> <BR> 0.1 moles/70 g, is 775 (Xmax = 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- <BR> <BR> <BR> <BR> <BR> diethyl-4-[(dodecylphenyl)-azo]-m-toluidine[(dodecylphenyl)- azo]-m-toluidine is 424 (Xmax = 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 1000).

In a second series of tests the marker concentrated com- positions 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 <BR> <BR> <BR> <BR> <BR> towards Xmax 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 extra- ction 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 pro- cess, as described hereinunder.

It has been found by the Applicant that formula (I) com- pounds wherein R1 = C4Hg are extractable also with aqueous acids (ex. HC1 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 Ri of formula (I) is a linear or branched alkyl having from 6 to 20 carbon <BR> <BR> <BR> <BR> atoms, said compounds having a specific absorbance E1% l 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 com- positions 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) : wherein: R is linear or branched alkyl with a number of carbon atoms from 6 to 20; -R2, R3, R4 and R5, 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 Rl= 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 com- positions having a high dry titre in organic solvents, com- prises the following steps: 1) diazotization, in hydroalcoholic solution of isopropyl alcohol, with nitrous acid of the primary aromatic amine having the R1 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 buf f ered 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 herein- after, which are not to be considered limitative of the scope of the same.

EXAMPLE 1 Synthesis of N-ethyl-N-(2-hydroxyethyl)-4-r (dodecylphenyl)- azol-m-toluidine (compound C) 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 HC1 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 20k NaNO2 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, 100 ml of water, 20 ml of HC1 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 dia- zonium 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 20k Na2CO3 (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 syn- thesis 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 vo- lumes of HC1 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 E1kl cm and Xmax values in isooctane and in the extraction solution are reported in Table I.

EXAMPLE 2 Synthesis of N, N-bis (2-hydroxyethyl)-4- [ (dodecylphenyl) azol-m- toluidine (compound D) The compound is synthetized according to the method de- scribed 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 HC1 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 re- sidue 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 65W.

EXAMPLE 2a Extraction test of the dye D concentrated liquid composition diluted with isooctane.

One proceeds as described in Example la.

The corresponding E1kl cm max values in isooctane and in the extraction solution are reported in Table I.

EXAMPLE 3 Synthesis of N, N-bis (2-hydroxvethyl)-4-[(dodecylphenyl) azol- aniline (compound B) 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 Ell 1 cm and Xmax values in isooctane and in the extraction solution are reported in Table I.

EXAMPLE 4 Synthesis of N-ethyl-N-(2-hydroxyethyl)-4-[(p-sec. butylphenyl- ) azol-m-toluidine (compound IB) sec. but- 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 50k.

EXAMPLE 4a Extraction test of dye IB concentrated liquid composition diluted with isooctane.

One proceeds as described in Example la.

The corresponding Ell cm and Xmax values in isooctane and in the extraction solution are reported in Table I.

EXAMPLE 5 (comparative) Synthesis of N, N-diethyl-4- [ (p-sec. butvlphenyl)-azol-m-tolui dine (compound IC) sec. but : 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 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 E1al cm and Xmax values in isooctane and in the extraction solution are reported in Table I.

EXAMPLE 6 (comparative) Synthesis of N, N-diethyl-4-[(dodecylphenyl)-azol-m-toluidine (compound IF) 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, 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-*5.

EXAMPLE 6a (comparative) Extraction test of the dye IF concentrated liquid composition diluted with isooctane.

One proceeds as described in Example la.

The corresponding Ell cm and AmaX 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 auto- traction 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 SmaX = 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 hydroal- coholic layer is clearly separated which colours red and which shows a spectrophotometric peak at Xmax = 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 Xmax = 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 compo- sition, 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 Xmax = 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 com- position, are treated and stirred with 40 ml of extraction acid solution consisting of 90 volumes of ethylenglycol and 10 volumes of HC1 10 N.

The limpid and red-coloured extraction solution is separated. It shows an absorption peak at Xmax = 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 so- lution of Example 11.

The limpid and red-orange-coloured extraction solution is separated. It shows an absorption peak at Xmax = 485 nm.

EXAMPLE 13 Preparation of the aminic copulating agent of formula (13A) 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 CH3ONa 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 HC1. 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) 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 Shellsol3 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 <BR> <BR> <BR> <BR> E1'6 cm and Xmax 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 HC1 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 Comparison among the specific absorbances E1kl cm °f invention markers determined at the maximum absorption wave length, respectively in isooctane and in the mixed organic/aqueous extraction solution with the specific @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ Product Isooctane Mixed solution aqueous/organic extraction solution E1% 1 cm #max E1% 1 cm # max IB 440 405 694 536 (ex. 4) B 411 399 735 540 (ex. 3) C 434 406 775 538 (ex. 1) D 429 405 752 541 (ex. 2) G 423 410 740 538 (ex. 14) IC 382 412 383 533 (ex. 5 comp.) IF 420 413 424 535 (ex.6 comp.) TABLE II Ratio between the specific absorbances E cm determined in the mixed aqueous/organic extraction @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ Ratio E1al cm IB/IC 1.81 B/IF 1.73 C/IF 1.82 D/IF 1. 77 G/IF 1.74