Fuel markers and methods of producing and using same

A method of determining adulteration of a fuel comprising:

• (i) acquiring a fuel sample, wherein the fuel sample comprises (a) a fuel, and (b) a compound characterized by Formula I:
• wherein X can be carbon (C), oxygen (O), or sulfur (S);
• wherein, when X is C, R1 and R2 can each independently be hydrogen, a C1 to C20 alkyl group, or a C6 to C10 aryl group, and wherein the C6 to C10 aryl group is a hydrocarbon;
• wherein, when X is O or S, R1 and R2 are lone non-bonding electron pairs;
• R3 and R3′ can each independently be hydrogen or a C1 to C4 alkyl group;
• R4 and R4′ can each independently be hydrogen, a C1 to C4 alkyl group, a C4 to C10 cycloalkyl group, or a C6 to C10 aryl group;
• R5 and R5′ can each independently be a C4 to C10 alkyl group;
• R6 and R6′ can each independently be hydrogen or a C1 to C6 alkyl group;
• and R7 and R7′ can each independently be hydrogen or a C1 to C4 alkyl group;
• (ii) adding a known amount of a heavy compound to the fuel sample to yield a marked fuel mixture, wherein the heavy compound comprises a compound of Formula I having at least one atom replaced with deuterium (2H), and wherein deuterium is present in the heavy compound in an amount greater than a natural abundance of deuterium;
• (iii) subjecting the marked fuel mixture to an analytical technique to record an analytical signal for the compound characterized by Formula I and an analytical signal for the heavy compound, wherein the heavy compound is used as an internal standard;
• (iv) comparing the analytical signal for the known amount of heavy compound to the analytical signal for the compound characterized by Formula I;
• (v) determining a ratio of an amount of the compound characterized by Formula I to the known amount of the heavy compound in the marked fuel mixture;
• and
• (vi) calculating the amount of the compound characterized by Formula I in the marked fuel mixture.

A method of determining adulteration of a fuel comprising:

• (i) subjecting to gas chromatography-mass spectrometry (GC-MS) a marked fuel mixture comprising (a) a fuel;
• (b) a compound characterized by Formula I:
• wherein X can be carbon (C), oxygen (O), or sulfur (S);
• wherein, when X is C, R1 and R2 can each independently be hydrogen, a C1 to C20 alkyl group, or a C6 to C10 aryl group, and wherein the C6 to C10 aryl group is a hydrocarbon;
• R3 and R3′ can each independently be hydrogen or a C1 to C4 alkyl group;
• wherein, when X is O or S, R1 and R2 are lone non-bonding electron pairs;
• R4 and R4′ can each independently be hydrogen, a C1 to C4 alkyl group, a C4 to C10 cycloalkyl group, or a C6 to C10 aryl group;
• R5 and R5′ can each independently be a C4 to C10 alkyl group;
• R6 and R6′ can each independently be hydrogen or a C1 to C6 alkyl group;
• and R7 and R7′ can each independently be hydrogen or a C1 to C4 alkyl group;
• and (c) a heavy compound, wherein the heavy compound comprises a compound of Formula I having at least one atom replaced with deuterium, wherein deuterium is present in the heavy compound in an amount greater than a natural abundance of deuterium, and wherein the heavy compound is used as an internal standard;
• (ii) recording GC-MS data for the compound characterized by Formula I and GC-MS data for the heavy compound in the marked fuel mixture;
• and
• (iii) determining a ratio of an amount of the compound characterized by Formula I to a known amount of the heavy compound in the marked fuel mixture.

A method of determining adulteration of a fuel comprising:

• (i) contacting a fuel sample with a heavy compound to form a marked fuel mixture, wherein the fuel sample comprises a fuel and a compound characterized by Formula I:
• wherein X can be carbon (C), oxygen (O), or sulfur (S);
• wherein, when X is C, R1 and R2 can each independently be hydrogen, a C1 to C20 alkyl group, or a C6 to C10 aryl group, and wherein the C6 to C10 aryl group is a hydrocarbon;
• wherein, when X is O or S, R1 and R2 are lone non-bonding electron pairs;
• R3 and R3′ can each independently be hydrogen or a C1 to C4 alkyl group;
• R4 and R4′ can each independently be hydrogen, a C1 to C4 alkyl group, a C4 to C10 cycloalkyl group, or a C6 to C10 aryl group;
• R5 and R5′ can each independently be a C4 to C10 alkyl group;
• R6 and R6′ can each independently be hydrogen or a C1 to C6 alkyl group;
• and R7 and R7′ can each independently be hydrogen or a C1 to C4 alkyl group;
• wherein the heavy compound comprises the compound of Formula I having at least one afoul replaced with deuterium (2H), and wherein deuterium is present in the heavy compound in an amount greater than a natural abundance of deuterium;
• (ii) subjecting the marked fuel mixture to solid phase extraction (SPE) to yield a marked fuel mixture fraction, wherein at least a portion of the compound characterized by Formula I and at least a portion of the heavy compound elute together in the marked fuel mixture fraction;
• and
• (iii) subjecting to an analytical technique the marked fuel mixture fraction to determine fuel adulteration, wherein the heavy compound is used as an internal standard.

A method of determining adulteration of a fuel comprising:

• (i) contacting a fuel sample with a heavy compound to form a marked fuel mixture, wherein the fuel sample comprises a fuel and a compound characterized by Formula I:
• wherein X can be carbon (C), oxygen (O), or sulfur (S);
• wherein, when X is C, R1 and R2 can each independently be hydrogen, a C1 to C20 alkyl group, or a C6 to C10 aryl group, and wherein the C6 to C10 aryl group is a hydrocarbon;
• wherein, when X is O or S, R1 and R2 are lone non-bonding electron pairs;
• R3 and R3′ can each independently be hydrogen or a C1 to C4 alkyl group;
• R4 and R4′ can each independently be hydrogen, a C1 to C4 alkyl group, a C4 to C10 cycloalkyl group, or a C6 to C10 aryl group;
• R5 and R5′ can each independently be a C4 to C10 alkyl group;
• R6 and R6′ can each independently be hydrogen or a C1 to C6 alkyl group;
• and R7 and R7′ can each independently be hydrogen or a C1 to C4 alkyl group;
• wherein the heavy compound comprises the compound of Formula I having at least one atom replaced with deuterium, and wherein deuterium is present in the heavy compound in an amount greater than a natural abundance of deuterium;
• (ii) subjecting the marked fuel mixture to solid phase extraction (SPE) to yield a marked fuel mixture fraction, wherein at least a portion of the compound characterized by Formula I and at least a portion of the heavy compound elute together in the marked fuel mixture fraction;
• and
• (iii) subjecting to gas chromatography-mass spectrometry (GC-MS) the marked fuel mixture fraction to determine fuel adulteration, wherein each of the compound characterized by Formula I and the heavy compound when subjected to GC-MS using electron ionization produces at least one ion having a amass-to-charge ratio of from about 300 to about 600 at an ionization energy of equal to or greater than about 70 eV, and wherein the heavy compound is used as an internal standard.