This invention relates to a new method for marking liquid hydrocarbons and other fuels and oils, as well as new compounds useful for this purpose.

Marking of petroleum hydrocarbons and other fuels and oils with various kinds of chemical markers is well known in the art. A variety of compounds have been used for this purpose, as well as numerous techniques for detection of the markers, e.g., absorption spectroscopy and mass spectrometry. For example, U.S. Pat. No. 9,587,187 discloses the use of trityl aryl ethers for use in marking liquid hydrocarbons and other fuels and oils. However, there is always a need for additional marker compounds for these products. Combinations of markers can be used as digital marking systems, with the ratios of amounts forming a code for the marked product. Additional compounds useful as fuel and lubricant markers would be desirable to maximize the available codes. The problem addressed by this invention is to find additional markers useful for marking liquid hydrocarbons and other fuels and oils.

STATEMENT OF INVENTION

The present invention further provides a method for marking a petroleum hydrocarbon or a liquid biologically derived fuel; said method comprising adding to said petroleum hydrocarbon or liquid biologically derived fuel at least one compound of formula (I)

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently are hydrogen, hydrocarbyl or hydrocarbyloxy; wherein each compound having formula (I) is present at a level from 0.01 ppm to 20 ppm.

The present invention is further directed to a compound of formula (II)

wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ ,R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ independently are hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy.

DETAILED DESCRIPTION

Percentages are weight percentages (wt%) and temperatures are in °C, unless specified otherwise. Experimental work is carried out at room temperature (20-25 °C), unless otherwise specified. Concentrations expressed in parts per million (“ppm”) are calculated on a weight/volume basis (mg/L). The term“petroleum hydrocarbon” refers to products having a predominantly hydrocarbon composition, although they may contain minor amounts of oxygen, nitrogen, sulfur or phosphorus; petroleum hydrocarbons include crude oils as well as products derived from petroleum refining processes; they include, for example, crude oil, lubricating oil, hydraulic fluid, brake fluid, gasoline, diesel fuel, kerosene, jet fuel and heating oil. Marker compounds of this invention can be added to a petroleum hydrocarbon or a liquid biologically derived fuel; examples of the latter are biodiesel fuel, ethanol, butanol, ethyl tert-butyl ether or mixtures thereof. A substance is considered a liquid if it is in the liquid state at 20°C. A biodiesel fuel is a biologically derived fuel containing a mixture of fatty acid alkyl esters, especially methyl esters. Biodiesel fuel typically is produced by

transesterification of either virgin or recycled vegetable oils, although animal fats may also be used. An ethanol fuel is any fuel containing ethanol, in pure form, or mixed with petroleum hydrocarbons, e.g.,“gasohol.” A“hydrocarbyl” group is a substituent derived from an aliphatic hydrocarbon, which may be linear, branched or cyclic and which may have one or more hydroxyl or alkoxy substituents. Preferably, hydrocarbyl groups are unsubstituted. An“alkyl” group is a substituted or unsubstituted saturated hydrocarbyl group having a linear, branched or cyclic structure. Alkyl groups may have one or more hydroxyl or alkoxy substituents. Preferably, alkyl groups are unsubstituted. Preferably, alkyl groups are linear or branched, i.e., acyclic. Preferably, each alkyl substituent is not a mixture of different alkyl groups, i.e., it comprises at least 98% of one particular alkyl group. An“alkenyl” group is a substituted or unsubstituted hydrocarbyl group having a linear, branched or cyclic arrangement and having at least one carbon-carbon double bond. Preferably, alkenyl groups have no more than three carbon-carbon double bonds, preferably no more than two, preferably one. Alkenyl groups may have one or more hydroxyl or alkoxy substituents.

Preferably, alkenyl groups are unsubstituted. Preferably, alkyl and alkenyl groups are linear or branched, i.e., acyclic. A“hydrocarbyloxy,”“alkoxy” or“alkenyloxy” group is a substituent formed by adding an oxygen atom at the point of attachment of a hydrocarbyl, alkyl or alkenyl group, respectively (e.g., between an alkyl group and a dibenzofuran carbon atom). The number of carbon atoms in a substituent includes any carbon atoms which may be in alkyl or alkoxy substituents thereof. Preferably, the compounds of this invention contain elements in their naturally occurring isotopic proportions.

Preferably, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ collectively have at least two carbon atoms, preferably at least three, preferably at least four. Preferably, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ collectively have no more than 60 carbon atoms, preferably no more than 50, preferably no more than 40, preferably no more than 30. Preferably, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ has at least two carbon atoms, preferably at least three, preferably at least four, preferably at least five. Preferably, hydrocarbyl groups are alkyl or alkenyl groups, preferably alkyl groups. Preferably, hydrocarbyloxy groups are alkoxy or alkenyloxy groups, preferably alkoxy groups.

Preferably, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently are hydrogen, C ₁ -C ₃₀ hydrocarbyl or C ₁ -C ₃₀ hydrocarbyloxy; preferably hydrogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₁ -C ₃₀ alkoxy or C ₂ -C ₃₀ alkenyloxy; preferably hydrogen, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₁ -C ₃₀ alkoxy or C ₂ -C ₃₀ alkenyloxy; preferably hydrogen, C ₁ -C ₂₅ alkyl or C ₂ -C ₂₅ alkenyl; preferably hydrogen, C ₁ -C ₂₂ alkyl or C ₂ -C ₂₂ alkenyl; preferably hydrogen or C ₁ -C ₂₂ alkyl; preferably hydrogen or Ci-Cis alkyl. Preferably, alkyl groups having at least 3 carbon atoms are linear or branched, i.e., not cyclic. In a preferred embodiment of the invention, R ² , R ⁴ , R ⁷ and R ⁹ are hydrogen. Preferably, R ¹ , R ⁵ , R ⁶ and R ¹⁰ independently are hydrogen or Ci-C ₆ alkyl, preferably hydrogen or Ci- C ₄ alkyl.

In using the compounds described herein as markers, preferably the minimum amount of each compound added to a liquid to be marked is at least 0.01 ppm, preferably at least 0.02 ppm, preferably at least 0.05 ppm, preferably at least 0.1 ppm, preferably at least 0.2 ppm. Preferably, the maximum amount of each marker is 50 ppm, preferably 20 ppm, preferably 15 ppm, preferably 10 ppm, preferably 5 ppm, preferably 2 ppm, preferably 1 ppm, preferably 0.5 ppm. Preferably, the maximum total amount of marker compounds is 100 ppm, preferably 70 ppm, preferably 50 ppm, preferably 30 ppm, preferably 20 ppm, preferably 15 ppm, preferably 12 ppm, preferably 10 ppm, preferably 8 ppm, preferably 6 ppm, preferably 4 ppm, preferably 3 ppm, preferably 2 ppm, preferably 1 ppm, preferably 0.5 ppm. Preferably, a marker compound is not detectible by visual means in the marked petroleum hydrocarbon or liquid biologically derived fuel, i.e., it is not possible to determine by unaided visual observation of color or other characteristics that it contains a marker compound.

Preferably, a marker compound is one that does not occur normally in the petroleum hydrocarbon or liquid biologically derived fuel to which it is added, either as a constituent of the petroleum hydrocarbon or liquid biologically derived fuel itself, or as an additive used therein.

Preferably, the marker compounds have a log P value of at least 3, where P is the l-octanol/water partition coefficient. Preferably, the marker compounds have a log P of at least 4, preferably at least 5. Log P values which have not been experimentally determined and reported in the literature can be estimated using the method disclosed in Meylan, W.M & Howard, P.H., J. Pharm. Set, vol. 84, pp. 83-92 (1995). Preferably the petroleum hydrocarbon or liquid biologically derived fuel is a petroleum

hydrocarbon, biodiesel fuel or ethanol fuel; preferably a petroleum hydrocarbon or biodiesel fuel; preferably a petroleum hydrocarbon; preferably crude oil, gasoline, diesel fuel, kerosene, jet fuel or heating oil; preferably gasoline. Preferably, the marker compound is added as a solution in a solvent, preferably a hydrocarbon solvent.

Preferably, the marker compounds are detected by at least partially separating them from constituents of the petroleum hydrocarbon or liquid biologically derived fuel using a chromatographic technique, e.g., gas chromatography, liquid chromatography, thin-layer chromatography, paper chromatography, adsorption chromatography, affinity chromatography, capillary electrophoresis, ion exchange and molecular exclusion chromatography. Chromatography is followed by at least one of: (i) mass spectral analysis, and (ii) FTIR. Identities of the marker compounds preferably are determined by mass spectral analysis. Preferably, mass spectral analysis is used to detect the marker compounds in the petroleum hydrocarbon or liquid biologically derived fuel without performing any separation. Alternatively, marker compounds may be concentrated prior to analysis, e.g., by distilling some of the more volatile components of a petroleum hydrocarbon or liquid biologically derived fuel.

Preferably, more than one marker compound is present. Use of multiple marker compounds facilitates incorporation into the petroleum hydrocarbon or liquid biologically derived fuel of coded information that may be used to identify the origin and other characteristics of the petroleum hydrocarbon or liquid biologically derived fuel. The code comprises the identities and relative amounts, e.g., fixed integer ratios, of the marker compounds. One, two, three or more marker compounds may be used to form the code. Marker compounds according to this invention may be combined with markers of other types, e.g., markers detected by absorption spectrometry, including those disclosed in U.S. Pat. No. 6,811,575; U.S. Pat. App. Pub. No. 2004/0250469 and EP App. Pub. No. 1,479,749. Marker compounds are placed in the petroleum hydrocarbon or liquid biologically derived fuel directly, or alternatively, placed in an additives package containing other compounds, e.g., antiwear additives for lubricants, detergents for gasoline, etc., and the additives package is added to the petroleum hydrocarbon or liquid biologically derived fuel.

In the compound of formula (II), preferably R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ independently are hydrogen or C1-C4 alkyl; preferably hydrogen or methyl, preferably hydrogen.

The compounds of this invention may be prepared by methods known in the art, e.g., allowing substituted phenols to react with a strong base and an aryl halide or diaryliodonium salt. EXAMPLES

Synthesis of Markers

Synthesis of l-isopropyl-2-phenoxybenzene (2) and l-(sec-butyl)-2-phenoxybenzene (3)

A 250 mL round bottomed flask was charged with zBuOK (1.809 g, 16.15 mmol) and THF (150 mL). The stirred mixture was cooled in an ice-bath and 2-isopropylphenyl (2.0 grams, 14.68 mmol) was slowly added over 2 minutes. The mixture was stirred at 0

°C for 15 min and diphenyliodonium triflate (7.57 g, 17.6 mmol) was added in 5 portions over 5 mins. The reaction was stirred at rt for 6 h. The reaction was quenched with H2O (150 mL). The contents were placed in a separatory funnel and extracted with Et ₂ 0 (250 mL). The organic phase was isolated, dried (Na ₂ S0 ₄ ), filtered, and concentrated. Purification was performed by column chromatography using hexane as the eluent. Yield

= 2.66 g, 85.5%. ¾ NMR (400 MHz, Chloroform-7) d 7.36 - 7.24 (m, 3H), 7.17 - 7.08 (m, 2H), 7.06 - 6.99 (m, 1H), 6.96 - 6.83 (m, 3H), 3.29 (p, J = 6.9 Hz, 1H), 1.22 (d, J = 6.9 Hz, 6H). ¹³ C NMR (101 MHz, Chloroform-7) d 158.49, 153.70, 140.39, 129.76, 127.10, 126.98, 124.32, 122.46, 120.00, 117.66, 27.20, 23.14.

Synthesis of l-(sec-butyl)-2-phenoxybenzene (3) was performed the same way but with 2-secbutylphenol. Yield = 59.8%. ¹ H NMR (400 MHz, Chloroform-7) d 7.35 - 7.24 (m, 3H), 7.17 - 7.08 (m, 2H), 7.07 - 6.98 (m, 1H), 6.96 - 6.83 (m, 3H), 3.05 (q, 7 = 7.1 Hz, 1H), 1.73 - 1.52 (m, 2H), 1.19 (d, 7 = 7.0 Hz, 3H), 0.82 (t, 7 = 7.4 Hz, 3H). ¹³ C NMR (101 MHz, Chloroform- 7) d 158.55, 154.09, 139.28, 129.72, 127.73, 126.90, 124.27, 122.40, 120.06, 117.67, 34.11, 30.21, 21.11, 12.38. Synthesis of 1 -isopropyl-4-phenoxybenzene (4)

A 40 mL Chem Glass vial was charged with the 4-isopropylphenol (4.0 g, 29.4 mmol) and ground KOH (1.38 g, 24.7 mmol). The mixture was heated for 10 minutes at 140 °C and all the KOH dissolved. The reaction cooled to rt over 5 minutes and CuCl (0.12 g, 1.2 mmol) and PhCl (4.6 g, 41.1 mmol) were added. The mixture was heated at 170 °C for 18 h. An aliquot was removed and analysis by ¹ H-NMR showed 14% conversion to the product. The reaction was worked up by treatment with CH2CI2 (100 mL) and 1 M HC1 (75 mL). The organic layer was isolated, dried with Na ₂ S0 ₄ , and filtered. The solvent was removed under reduced pressure and the product was purified via column chromatography over a 100 g Biotage silica column using hexanes. Yield = 1.1 g, 21%. ¾ NMR (400 MHz, Chloroform-^/) d 7.35 - 7.24 (m, 3H), 7.17 - 7.08 (m, 2H), 7.07 - 6.98

(m, 1H), 6.96 - 6.83 (m, 3H), 3.05 (q, J = 7.1 Hz, 1H), 1.73 - 1.52 (m, 2H), 1.19 (d, J = 7.0 Hz, 3H), 0.82 (t, J = 7.4 Hz, 3H). ¹³ C NMR (101 MHz, Chloroform- ) d 158.55, 154.09, 139.28, 129.72, 127.73, 126.90, 124.27, 122.40, 120.06, 117.67, 34.11, 30.21, 21.11, 12.38.

Synthesis of 4, 4’-oxybis( isopropylbenzene) (5) and 2,2’-oxybis(isopropylbenzene) (6)

A 40 mL Chem Glass vial was charged with 4-isopropylphenol (2.45 g, 18.0 mmol) and ground KOH (0.85 g, 15.1 mmol). The mixture was heated for 20 minutes at 140 °C with vigorous stirring. The reaction was cooled to rt over 10 minutes and CuCl (0.071 g, 0.072 mmol) and l-bromo-4-isopropylbenzene (5.0 g, 25.2 mmol) were added. The vial was capped and the mixture was heated at 190 °C for 5 hours. The reaction was worked up by pouring the contents into a separatory funnel with water (100 mL) and CH2CI2 (100 mL). The organic layer was isolated, dried (MgS0 ₄ ), and filtered. Product was purified by column chromatography using a 50 g Biotage column and a gradient of 0 to 15% CH2CI2 in hexane over 12 columns. Compound eluted from 4 to 8 column lengths. Isolated yield was 1.9 g., yield based on KOH was 49.6%. ¹ H NMR (400 MHz, Chloroform- 7) d 7.23 - 7.10 (m, 4H), 6.98 - 6.85 (m, 4H), 2.88 (hept, 7 = 6.9 Hz, 2H), 1.23 (d, J = 7.0 Hz, 12H). ¹³ C NMR (101 MHz, Chloroform-7) d 155.59, 143.61, 127.60,

118.71, 33.59, 24.30.

Synthesis of 2,2'-oxybis(isopropylbenzene) (6) was performed the same way but with 2- isopropylphenol and l-bromo-2-isopropylbenzene. Yield was 45.2% based on KOH. ¹ H NMR (400 MHz, Chloroform-7) d 7.39 - 7.28 (m, 2H), 7.15 - 7.01 (m, 4H), 6.76 - 6.67 (m, 2H), 3.36 (hept, J = 6.9 Hz, 2H), 1.27 (d, J = 6.9 Hz, 12H). ¹³ C NMR (101 MHz, Chloroform-7) d 154.83, 139.36, 126.89, 126.87, 123.30, 118.02, 27.42, 23.06.

Synthesis of l-phenoxy-4-(2,4,4-trimethylpentan-2-yl)benzene (7)

A 250 mL round bottomed flask was charged with zBuOK (2.38 g, 2l.3mmol) and THF (150 mL). The stirred mixture was cooled in an ice-bath and t-octylphenol (4.0 grams, 19.4 mmol) was slowly added over 2 minutes. The mixture was stirred at 0 °C for 15 min and diphenyliodonium triflate (10 g, 23.3 mmol) was added in 5 portions over 5 mins. The reaction was stirred at rt for 3 h. The reaction was quenched with H ₂ 0 (150 mL). The contents were placed in a separatory funnel and extracted with Et ₂ 0 (250 mL). The organic phase was isolated, dried (Na ₂ S0 ₄ ), filtered, and concentrated. Purification was performed by column chromatography using hexane as the eluent. Yield = 3.2 g, 58%. ¾ NMR (400 MHz, Chloroform- ) d 7.41 - 7.26 (m, 4H), 7.10 - 6.89 (m, 5H), 1.72 (s, 2H), 1.37 (s, 6H), 0.73 (s, 9H). ¹³ C NMR (101 MHz, Chloroform-^/) d 157.79, 154.43, 145.22, 129.64, 127.44, 122.78, 118.47, 118.38, 57.11, 38.23, 32.40, 31.80, 31.66.

Synthesis of l-(pentadecyl)-3-phenoxybenzene (8)

8

A 250 mL round bottomed flask was charged with zBuOK (1.6 g, 14.4 mmol) and THL (l50mL) and the flask was cooled in an ice -bath. To this stirred suspension, 3- pentadecylphenol (4 grams, 13.1 mmol) was slowly added over 2 minutes. The mixture was stirred at 0 C for 15 min and diphenyliodonium triflate (6.8 g, 15.8 mmol) was added in 5 portions over 5 mins. The reaction was stirred at RT for 3 h. The reaction was quenched with H ₂ 0 (150 mL). The contents were placed in a separatory funnel and extracted with Et ₂ 0 (250 mL). The organic phase was isolated, dried (Na ₂ S0 ₄ ), filtered, and concentrated. Purification was performed by column chromatography using hexane as the eluent. Isolated yield was 2.85 g, 57% ¹ H NMR (400 MHz, Chloroform-^/) d 7.32 (td, J = 7.9, 2.5 Hz, 2H), 7.27 - 7.18 (m, 1H), 7.08 (dd, J = 8.6, 6.2 Hz, 1H), 7.05 - 6.98 (m, 2H), 6.92 (d, J = 7.4 Hz, 1H), 6.89 - 6.76 (m, 2H), 2.65 - 2.50 (m, 2H), 1.59 (t, J = 7.5 Hz, 2H), 1.26 (d, J = 4.5 Hz, 24H), 0.88 (dd, J = 8.4, 5.8 Hz, 3H). ¹³ C NMR (101 MHz, Chloroform- ) d 157.62, 157.22, 145.22, 129.80, 129.54, 123.58, 123.11, 119.19,

118.86, 116.26, 35.99, 32.09, 31.47, 29.86, 29.83, 29.75, 29.70, 29.64, 29.53, 29.43,

22.86, 14.27.

Laundering of 7, 8, and Analysis

Samples were made at a 3 mg/l concentration in diesel that was treated with basic alumina and filtered. The marked diesel sample was mixed with laundering agent in the desired ratio. A magnetic stir bar was added to the sample and arranged on a multi position magnetic stir plate. All samples were stirred for 4 hours at 200 rpm. After four hours all samples were let to settle for 30 minutes. An aliquot was taken from the top and filtered through 0.45 micron PTFE filter. Laundered samples along with controls that were not exposed to laundering were analyzed by GC/MS with the parameters below

Agilent 6890 Gas Chromatograph

Autosampler: Agilent 7683B Series

Detector: Agilent MSD 5973N mass spectroscopy detector

Column: DB-35MS, l5-m x 0.25-mm ID, 0.25-pm film

Oven: Initial temperature 100 °C

Ramp 1 at 10 °C/minute to 280 °C, hold 0 min

Ramp 2 at 10 °C/minute to 320 °C, hold 5 min

Injection port: 280 °C

Transfer line: 280 °C

Injection Mode: Splitless

Carrier gas: Helium

Column flow rate: 1.4 mL/min, constant flow mode

Purge time: 20 min

Purge flow: 20 mL/min

Viscosity delay: 1

Injection volume: 1 pL

Acquisition mode: SIM

Solvent delay: 13 min

MS quad: 200 °C

MS source: 250 °C

11 Laundering Agent Comments 8 7

Al Oxide-Neutral 5 % w/v 95.1 93.5

Al Oxide-Basic 5 % w/v 105.1 103.4

Bentonite 5 % w/v 103.2 107.8

HCI Cone. 5 % w/v 102.6 101.2

Fuller's Earth 5 % w/v 101.3 99.5

H2O2 -30 % 50 v/v 101.3 96.1

Silica Gel 5 % w/v 106.8 100.6

Bleach (commercial) 5 % w/v 103.9 101.6

Activated carbon 5 % w/v 98.9 95.8

Methanol 50 % v/v 120.2 106.3

Acetonitrile 50 % v/v 118.5 103.9

H2SO4 Cone. 5 % w/V 105.3 107.1

HNO3 Cone. 5 % w/v 100.3 106.8

Laundering diphenyl ether (1), 2-6, and Analysis Samples of 1-6 were made at 10 mg/l concentration in diesel that was treated with basic alumina and filtered. The marked diesel samples were mixed with laundering agent in the specified ratio. A magnetic stir bar was added to the sample and arranged on a multi position magnetic stir plate. All samples were stirred for 4 hours at 200 rpm. After four hours all samples were let to settle for 30 minutes. An aliquot was taken from top and filtered through syringe with 0.45 micron PTFE filter. Laundered samples along with control which was not exposed to laundering were analyzed by GC/MS as described below

Quantitative analysis and separation of fuel markers from fuel matrix was achieved with two-dimensional heartcutting gas chromatography method. A Deans Switch based on capillary flow technology is used to afford in-oven heartcutting capability. The method employs a DB-17HT column (15 m x 250 pm x 0.15 pm) in the first dimension (Dl) and a VF-WAXms column (30 m x 250 pm x 1.0 pm) in the second dimension (D2). A flame ionization detector (FID) was used as the detector in Dl and a mass selective detector (MSD) was used for low level detection of markers the D2 column using single-ion monitoring (SIM) mode. The retention times of the markers in Dl which determine the heartcutting time was obtained using standards in xylenes. The full mass spectra of the individual markers were obtained to determine the most selective ion fragment that gave the best sensitivity and selectivity for analysis of markers in fuel matrix. Quantitation was performed using multi-point external calibration.