KR20060018801A - Lactone-based labeling substance having a double bond ester group, method for labeling and detecting the same - Google Patents

Abstract

The present invention relates to a lactone-based labeling substance having a double bond ester group, a method for labeling and detecting the same, and more particularly, a method and labeling for adding a lactone-based substance having an unsaturated double bond ester group to oil to cover the oil product. The present invention relates to a method for detecting a UV / VIS region or an IR region by adding a coloring agent having a function of inducing a specific color to the oil product, and the labeling substance.

Lactone-based label, double bond ester group, phenolphthalein dioleate

Description

Lactone marker comprising double bond ester group and method for markng and detecting the same}

FIG. 1 shows a graph of quantitative analysis of petroleum phthalate dioleate at a concentration of 1 to 50 ppm using a UV / VIS spectrometer.

Figure 2 shows a graph quantifying petroleum labeling thymolphthalein diacrylate at a concentration of 1 to 50ppm using a UV / VIS spectrometer.

Figure 3 shows a graph quantifying the petroleum labeling naphtholphthalein dioleate at a concentration of 1 to 50ppm using a UV / VIS spectrometer.

The present invention relates to a lactone-based labeling substance having a double bond ester group, a method of labeling and detecting the same, and more particularly, a method of adding a lactone-based substance having an unsaturated double bond ester group to oil to conceal the label in an oil product, and The present invention relates to a method for detecting a UV / VIS region or an IR region by adding a coloring agent having a function of inducing a specific color to a labeled oil product, and the labeling substance.

Petroleum identifiers (labels, markers) have been developing since the 1980s. Petroleum identifiers are added and used for two reasons:

First, crude oil has been used to prevent environmental pollution and the shortening of lifespan of automobiles caused by illegal use of petroleum. This is being introduced and implemented to prevent the use of fake gasoline and to prevent the illegal use of special purpose duty-free oil.

Second, due to the advancement of petroleum refining technology due to the development of petrochemical technology, a lot of costs are used for quality competition and maintenance of each refiner. As a result, the introduction of petroleum identifiers for the branding and maintenance of quality of each refiner is being carried out, which is beginning to be added to gasoline and expanded to LPG and diesel.

Such petroleum addition identifiers can be classified into three types as follows: (1) As an identifier developed and used in the early stage, aromatic amine is added, extracted with diazot solution, and quantitatively determined. (Reference: U.S. Patent 4,209,302), Aromatic Compounds with Diazo Groups (Reference: U.S. Patent 5,156,653, U.S. Patent 5,252,103, European Patent 0803563) US Patent 4,764,474); (2) a method of quantitating and qualitifying with alkylammonium after adding a fluorescein-based or phthalane-based (see US Patent No. 5,672,182, US Patent No. 5,498,808) substance as an ester substance having a saturated alkyl group; (3) A method using a phthalocyanine-based compound analyzed in the near infrared region (US Pat. No. 6,312,958) and a method using a phthalate ester compound that can be analyzed in the infrared field (US Pat. No. 5,984,983).

The above-mentioned fluorescent identifier was used as an identifier by introducing a saturated alkyl ester group, and the economic efficiency was lowered by using a relatively expensive enzyme (for example, International Publication No. WO2001 / 00561) as a coloring agent, or an alkylammonium hydroxide ( For example, US Pat. No. 5,672,182) is used, causing discomfort due to the smell of ammonia. In addition, there is a disadvantage in that octylpyrrolidone, which is a relatively expensive solvent, is used when using an identifier in the form of a saturated alkyl ester (for example, US Pat. No. 5,498,808).

The technical problem to be achieved by the present invention is to provide a labeling material suitable for the identification of oil products.

Another object of the present invention is to label an oil product with a lactone-based unsaturated ester labeling substance and provide an oil product identification method for detecting the same in a UV / VIS region or an IR region.

The present invention to achieve the above technical problem,

It provides a lactone-based label of the general formula (1):

<Formula 1>

In the above formula,

R ₁ to R ₁₄ are each independently hydrogen, nitro group, halogen, carboxyl group, amino group, substituted or unsubstituted C1-30 alkyl group, substituted or unsubstituted C2-30 alkenyl group, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 30 carbon atoms Represent;

R ₅ and R ₆ , R ₇ and R ₈ , R ₁₀ and R ₁₁ , or R ₁₂ and R ₁₃ may be bonded to each other independently to form a fused ring;

Provided that at least one of R ₉ and R ₁₄ represents a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms.

The present invention to achieve the above other technical problem,

Labeling an oil product using the lactone-based labeling material of Formula 1; And

The present invention provides a method for identifying an oil product, the method comprising: detecting and labeling the labeled oil product with an alkanol metal salt.

Hereinafter, the present invention will be described in more detail.

The present invention provides a lactone-based label of the general formula (1):

<Formula 1>

Wherein R ₁ to R ₁₄ are as defined above.

The labeling substance of Chemical Formula 1 according to the present invention has increased solubility in oil products, and it is possible to use a low cost colorant, but does not cause odor.

In the case of general lactone compounds, since they are polar and have poor solubility in non-polar common oil products, introduction of non-polar groups is essential in order to use them as markers for oil products. It is possible to improve the solubility in oil products by introducing an ester group having at least one unsaturated double bond to further enhance the nonpolarity of the lactone compound. In addition, it does not emit strong volatile substances such as ammonia and does not cause off-flavor, and because of high solubility in oil products, there is no need to use expensive solvents, thereby improving economic efficiency.

The compound of Formula 1 as described above may be prepared by using a phthalein-based compound as a starting material and introducing an unsaturated double bond ester group thereto, but is not limited thereto, and may be prepared through conventional methods known in the art. It can manufacture. This is due to the fact that the melting point of the unsaturated alkyl acid derivatives is lower than that of the saturated alkyl acid derivatives (for example, the melting point of stearic anhydride; 70 to 72 ° C.), compared to using conventional saturated alkyl acid anhydrides for the introduction of nonpolar groups. Melting point of oleic anhydride; 22 to 24 ℃) it is possible to introduce an ester group having an unsaturated double bond to the phthalein-based starting material.

As such a compound of General formula (1), the compound of following General formula (2) or 3 is mentioned.

<Formula 2>

In the above formula,

R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , and R ₁₃ each independently represent hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,

R ₉ and R ₁₄ each independently represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms,

Provided that at least one of R ₉ and R ₁₄ is a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms.

<Formula 3>

In the above formula,

R ₉ and R ₁₄ each independently represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms,

Provided that at least one of R ₉ and R ₁₄ is a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms.

As the compound of Chemical Formula 2, a compound of the following Chemical Formulas 4 to 9 is preferable.

<Formula 4>

<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

<Formula 10>

Among the above formulas,

R ₉ and R ₁₄ each independently represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms,

Provided that R ₉ and R ₁₄ At least one of is a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms.

In the present invention, when R ₉ or R _{14, which} is a substituent of the labeling substance of Formula 1, is a functional group having an unsaturated double bond, for example, acryl, crotonyl, methacryl, hexenyl, octenoyl, oleyl, and the like Among these, methacryl and oleoyl are more preferable.

The above-described labeling substances according to the present invention may be added to various oil products, for example, gasoline, diesel, fuel oil, kerosene, etc. More specifically, gasoline for automobiles, liquefied natural gas for automobiles, liquefied petroleum gas In addition, there are heavy oil for various prime movers, and various kinds of fuel oil (kerosene), liquefied natural gas for fuel, liquefied petroleum gas, and important products for fuel are also available.

Therefore, by using the labeling material according to the present invention, including gasoline produced by a non-legal supplier including a trademark owner of oil products, as well as fake gasoline manufactured by mixing chemicals such as benzene, toluene, solvent, etc. All oil products such as prime movers and fuels can be identified.

Since the labeling substance according to the present invention described above is used in a small amount with respect to the oil product, it hardly affects the performance of the oil product. In addition, since the solubility in these products is high, there is little possibility of forming it as sludge or sediment in the use process of oil products, and it hardly damages the machinery etc. which use these oil products as a raw material. Since the content of the labeling substance according to the present invention for the oil product can be detected even in a small amount, it is preferable to add 0.01 to 100 ppm, preferably 0.03 to 30 ppm, more preferably 0.05 to 10 ppm with respect to the oil product. When the content of the labeling material is less than 0.01ppm, it may be difficult to detect due to the small amount of color development by the coloring agent, and when it exceeds 100ppm, there is a problem in that it is economically undesirable because there is no benefit of coloration due to the excess content.

On the other hand, the above-described labeling material of the present invention, since the colors of different wavelengths appear depending on the form of the substituents, if they are used alone or in combination of two or more of the labeling materials in a predetermined ratio so that they display the color at the same time It is possible to label in different colors for each product. Therefore, even in the case of mixing and using the same kind of labeling material, it is possible to commercialize and use various labeling materials having various relative concentrations just by adjusting their mixing ratio. These labels can be added to the oil product in solid form such as powders or crystals or in liquid form such as concentrates. It is usually better to use liquid form for handling problems.

In order to prepare a liquid concentrate containing the labeling substance according to the present invention, the labeling substance may be dissolved or diluted in an organic solvent to prepare a non-aqueous solution having high solubility in oil products. In general, solvents suitable for use with liquid petroleum products are aromatic and aprotic solvents. For example, aromatic hydrocarbons (eg alkyl benzenes such as xylene and naphthalene), aromatic alcohols (eg benzyl alcohol) and aromatic substituted alkanols (eg phenol glycol ether) can be preferably used. Aprotic solvents include formamide, N, N-dimethylformamide, N, N-dimethyl acetamide, 1-methyl pyrrolidinone, 1-octyl pyrrolidinone, 1-dodecyl pyrrolidinone and the like. 1-octyl pyrrolidinone solvent is a particularly preferred aprotic solvent. These solvents may be used alone or in combination.

The labeling substances according to the present invention are colorless or substantially colorless, and since they are soluble in oil products, they are detected by adding a coloring agent to the oil products labeled therein and reacting with the labeling substances to develop color.

As a colorant usable in the present invention, it is preferable to use alkanol metal salts, such as alkanol lithium salts, alkanol sodium salts, or alkanol potassium salts, which allow discoloration of the entire oil product. . Examples of the alkanols include methanol, ethanol, butanol, t-butanol and 2-ethylhexanol, and sodium methoxide, lithium methoxide and potassium methoxide are particularly preferable.

Coloring agents such as the alkanol metal salts enable discoloration of oil products by hydrolyzing ester bonds in the labeling material according to the invention and removing hydrogen in the structure of the phthaleinhydroxy group. The discoloration of the oil product is able to qualitatively and quantitatively analyze the presence and concentration of the labeling substance by detecting absorbance occurring in the UV / VIS region.

The coloring process by the coloring agent is described in detail as follows.

Until the expression using the coloring agent, the labeling substance of Formula 1 according to the present invention is colorless or substantially colorless, and when the coloring agent according to the present invention is added to an oil product at a predetermined ratio, The labeling substance of Formula 1 is converted into a colored anionic form. For example, ester groups having unsaturated double bonds are believed to be hydrolyzed by a colorant base and then ionized to form oxygen anion (O ⁻ ) groups. The presence of these anions causes the oil products to have a strong color. Furthermore, as the ester moiety having the unsaturated double bond is removed and a charged ion is formed, the color becomes negative resonance. This is because the labeling material of Formula 1 is not easily extracted from an organic medium such as an oil product, whereas the color expression form of the labeling material of Formula 1 can be quantified because the entire petroleum layer is colored.

Therefore, since the labeling substances according to the present invention can also be quantitatively analyzed, when a fake gasoline is prepared by diluting with a solvent such as toluene or benzene, it is possible to easily check the authenticity thereof. That is, when a labeling substance having a predetermined concentration is added to the oil product, when a concentration lower than the concentration is quantitatively detected at a later detection, it may be easily determined whether the product is diluted.

On the other hand, using an infrared analyzer, it is possible to analyze the carbonyl group (wavelength 1680 ~ 1880cm ^-1 ) irrespective of the addition of a coloring agent, it is possible to qualitative and quantitative analysis that is impossible in the infrared analysis of the existing identifier.

The alkyl group which is a substituent used in the compound of the present invention includes a straight or branched radical having 1 to 30 carbon atoms, and preferably includes a straight or branched radical having 1 to about 12 carbon atoms. More preferred alkyl radicals are lower alkyl having 1 to 6 carbon atoms. Examples of such radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, iso-amyl, hexyl and the like. Even more preferred are lower alkyl radicals having 1 to 3 carbon atoms.

The alkenyl group, which is a substituent used in the compound of the present invention, refers to a C 2 to C 30 straight or branched aliphatic unsaturated hydrocarbon group containing a carbon-carbon double bond. Preferred alkenyl groups have 2 to 20 carbon atoms in the chain, more preferably 4 to 18 carbon atoms in the chain. Branched means that one or more lower alkyl or lower alkenyl groups are attached to the alkenyl straight chain. Such alkenyl groups may be unsubstituted or may be independently substituted by one or more groups including, but not limited to, halo, carboxy, hydroxy, formyl, sulfo, sulfino, carbamoyl, amino and imino. Examples of such alkenyl groups include ethenyl, propenyl, carboxyethenyl, carboxypropenyl, sulfinoethenyl, sulfonoethenyl and the like.

The aryl group, which is a substituent used in the compound of the present invention, may be used alone or in combination to mean a carbocyclic aromatic system having 6 to 30 carbon atoms including one or more rings, and the rings may be attached or fused together by a pendant method. Can be. The term aryl includes aromatic radicals such as phenyl, naphthyl, tetrahydronaphthyl, indane and biphenyl. More preferred aryl is phenyl. The aryl group may have 1 to 3 substituents such as hydroxy, halo, haloalkyl, nitro, cyano, alkoxy and lower alkylamino.

The heteroalkyl group which is a substituent used in the compound of the present invention includes one, two, or three heteroatoms selected from N, O or S, and represents a case where the remaining atoms constituting the chain are carbon atoms. The rest is as defined for the alkyl group.

The heteroalkenyl group, which is a substituent used in the compound of the present invention, includes one, two, or three heteroatoms selected from N, O, or S, and represents a case where the remaining atoms constituting the chain are carbon atoms. Otherwise, the definition is the same as for the alkenyl group.

The heteroaryl group, which is a substituent used in the compounds of the present invention, includes 1, 2 or 3 heteroatoms selected from N, O or S, and the remaining ring atoms are C 1 to monovalent monocyclic or 6 to 20 ring atoms or It means acyclic aromatic radical. The term also refers to monovalent monocyclic or bicyclic aromatic radicals in which heteroatoms in the ring are oxidized or quaternized, for example to form N-oxides or quaternary salts. Representative examples include thienyl, benzothienyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, quinoxalinyl, imidazolyl, furanyl, benzofuranyl, thiazolyl, isoxazolyl, Benzisoxazolyl, Benzimidazolyl, Triazolyl, Pyrazolyl, Pyrrolyl, Indolyl, 2-pyridonyl, 4-pyridonyl, N-alkyl-2-pyridonyl, Pyrazinonil, Pyridazino Nil, pyrimidinyl, oxazoloyl, and their corresponding N-oxides (eg, pyridyl N-oxides, quinolinyl N-oxides), quaternary salts thereof, and the like.

The fused ring used in the compound of the present invention refers to a state in which two adjacent functional groups combine with each other to form a ring, and these formed rings share two carbon atoms with the adjacent ring. A ring formed by combining two functional groups may form a substituted or unsubstituted 5 to 5 membered aryl group or heteroaryl group having 5 to 30 carbon atoms.

<Example>

Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these.

Preparation Example 1 Synthesis of 2-sec-Butylphenolphthalein

10 g of phthalic anhydride and 30.4 g of 2-sec-butylphenol were added to a 100 ml three-necked reactor and stirred under nitrogen. 15 g of methanesulphonic acid and 5 g of anhydrous zinc chloride were added here, and it heated up at 120 degreeC. After the reaction for 14 hours, the reactant was added to 200 g of water to remove the filtrate. Then, 30 ml of methylene chloride and 30 g of 50% aqueous sodium hydroxide solution were added to the organic layer, and then the aqueous layer was separated. The aqueous solution was neutralized with acid, extracted with methylene chloride and concentrated to give 15.14 g (yield: 52.1%) of yellow 2-sec-butylphenolphthalein.

Preparation Example 2 Synthesis of 2-tert-Butylphenolphthalein

14.97g of 2-tert-butylphenolphthalein (yield: 51.5%) by the same procedure as in Preparation Example 1, except that 30.4 g of 2-tert-butylphenol was used instead of 2-sec-butylphenol in Preparation Example 1. )

Preparation Example 3 Synthesis of 2,6-di-tert-butylphenolphthalein

2,6-di-tert-butyl was prepared by the same procedure as in Preparation Example 1, except that 41.8 g of 2,6-di-tert-butylphenol was used instead of 2-sec-butylphenol in Preparation Example 1. Phenolphthalein 14.87 (yield: 40.6%) was obtained.

Preparation Example 4 Synthesis of 2,6-di-sec-butylphenolphthalein

2,6-di-tert-butyl was prepared in the same manner as in Preparation Example 1, except that 41.8 g of 2,6-di-sec-butylphenol was used instead of 2-sec-butylphenol in Preparation Example 1. 16.55 g (yield: 45.2%) of phenolphthalein were obtained.

Example 1 Synthesis of Phenolphthalein Dioleate

<Formula 4-a>

1.22 g of phenolphthalein, 30 ml of methylene chloride, and 0.85 g of triethylamine were added to a 100 ml three-neck reactor, and the mixture was stirred at 7 ° C. or lower for 30 minutes. 4 ml of 70% oleoyl chloride was added dropwise thereto for 1 hour using a dropping funnel. Thereafter, the mixture was maintained at 10 ° C. or lower for 3 hours, maintained at room temperature for 24 hours, and then 50 ml of distilled water was added and the layers were separated. The organic layer was added 5 ml of 0.1 N hydrochloric acid, and then the layers were separated, and the organic layer was neutralized with 5% sodium carbonate solution. The methylene chloride of the obtained organic layer was dried over anhydrous magnesium sulfate as a drying agent and filtered. The methylene chloride of the organic layer was removed under reduced pressure, and then concentrated in vacuo to give 3.1 g of brown phenolphthalein dioleate (yield: 95.1%).

¹ H NMR (400 MHz, CDCl ₃ ): δ = 0.90 (m, 6H, CH ₃ ), 1.30-1.36 (m, 44H, CH ₂ ), 2.04 (m, 8H, CH ₂ (allyl)), 2.58 (t , 4H, CH ₂ ), 5.34 to 5.53 (m, 4H, CH = CH), 7.11 (d, 4H, phenolic), 7.38 (d, 4H, phenolic), 7.59 (m, 2H, aromatic), 7.74 (t , 1H, aromatic), 7.97 (d, 1H, aromatic)

IR (cm ^-1 ): 2924, 1774, 1607, 1463, 1164

Example 2: Synthesis of Orthocresolphthalein Dicrotonylate

<Formula 5a>

2.8 g of orthocresolphthalein, 1.9 g of triethylamine, and 30 ml of methylene chloride were added to a 100 ml three-necked reactor, and the mixture was stirred while maintaining 5 ° C. A mixed solution of 2 ml of 90% crotonyl chloride and 10 ml of methylene chloride was added dropwise thereto using a dropping apparatus for 1 hour. Thereafter, the mixture was maintained at 10 ° C. or lower for 3 hours, and then maintained at room temperature for 21 hours, and 50 ml of distilled water was added thereto to separate the layers. 4 ml of 1N hydrochloric acid was added to the organic layer, and the layers were separated. The organic layer was neutralized with 5% sodium carbonate solution. The methylene chloride of the obtained organic layer was dried over magnesium sulfate anhydride as a drying agent, and filtered. The methylene chloride of the organic layer was removed under reduced pressure, and then concentrated in vacuo to give 3.25 g (yield: 82.5%) of a yellow target product.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 2.01 (m, 6H, CH ₃ ), 2.17 (s, 6H, CH ₃ ), 5.87 (d, 2H, CH = CH), 6.11 (d, 2H, CH = CH), 7.03 (d, 2H, phenolic), 7.18-7.26 (m, 4H, phenolic), 7.59-7.61 (m, 2H, aromatic), 7.74 (t, 1H, aromatic), 7.97 (d, 1H, aromatic)

IR (cm ^-1 ): 2916, 1770, 1650, 1463, 1122

Example 3: Synthesis of thymolphthalein diacrylate

<Formula 6a>

2.55 g of thymolphthalein, 1.42 g of triethylamine, and 30 ml of methylene chloride were added to a 100 ml three-necked reactor, and stirred at 5 ° C. Here, a mixed solution of 1 ml of acryloyl chloride and 10 ml of methylene chloride was added dropwise for 1 hour using a dropping apparatus. Thereafter, the same process as in Example 2 was carried out to obtain 2.65 g (yield: 87.5%) of thymolphthalein diacrylate as a target product.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.08 (m, 6H, CH ₃ ), 2.12 (s, 6H, CH ₃ ), 6.04 (d, 2H, CH = CH), 6.37 (t, 2H, CH = CH), 6.62 (d, 2H, CH = CH), 6.91 (s, 2H, phenolic), 7.01 (s, 2H, phenolic), 7.41 (d, 1H, aromatic), 7.63 (t, 1H, aromatic) , 7.74 (t, 1H, aromatic), 8.01 (d, 1H, aromatic)

IR (cm ^-1 ): 2966, 1774, 1638, 1463, 1153

Example 4 Synthesis of 2-sec-Butylphenolphthalein Dimethacrylate

<Formula 7a>

3.24 g of 2-sec-butylphenolphthalein, 1.67 g of triethylamine, and 30 ml of methylene chloride were added thereto, and the mixture was stirred at 5 ° C. Here, a mixed solution of 2 ml of 80% methacroyl chloride and 10 ml of methylene chloride was added dropwise for 1 hour using a dropping apparatus. Thereafter, the same process as in Example 2 was performed to obtain 3.49) g (yield: 82.1%) of 2-sec-butylphenolphthalein dimethacrylate.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 0.85 (m, 6H, CH ₃ ), 1.22 (s, 6H, CH ₃ ), 1.59 (q, 4H, CH ₂ ), 5.79 (s, 2H, CH = CH), 6.38 (s, 2H, CH = CH), 6.91 (s, 2H, phenolic), 7.04 (d, 2H, phenolic), 7.14 (d, 2H, phenolic), 7.41 (d, 1H, aromatic), 7.59 (m, 1H, aromatic), 7.74 (t, 1H, aromatic), 7.98 (d, 1H, aromatic)

IR (cm ^-1 ): 2955, 1766, 1677, 1448, 1130

Example 5: Synthesis of 2,6-di-sec-butylphenolphthalein diacrylate

<Formula 8a>

2,6-disec-butylphenolphthalein diacrylate 0.44 was subjected to the same molar ratio and process as Example 3, except that 0.41 g of 2,6-di-sec-butylphenolphthalein was used instead of 2.55 g of thymolphthalein. g, yield: 89.5%.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 0.78 to 0.85 (m, 12H, CH ₃ ), 1.11 to 1.22 (m, 12H, CH ₃ ), 1.54 (q, 8H, CH ₂ ), 6.05 (d, 2H, CH = CH), 6.38 (d, 2H, CH = CH), 6.93 (s, 2H, CH = CH), 7.05 (s, 4H, phenolic), 7.41 (d, 1H, aromatic), 7.59 (m , 1H, aromatic), 7.99 (t, 1H, aromatic), 8.31 (d, 1H, aromatic)

IR (cm ^-1 ): 2970, 1751, 1634, 1463, 1149

Example 6 Synthesis of 2-tert-Butylphenolphthalein Diacrylate

<Formula 9a>

0.82 g of 2-tert-butylphenolphthalein diacrylate (yield: 70.3%) was subjected to the same molar ratio and process as Example 3, except that 2.4 g of 2-tert-butylphenolphthalein was used instead of 2.55 g of thymolphthalein. Got.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.34 (m, 18H, CH ₃ ), 6.04 (d, 2H, CH = CH), 6.37 (t, 2H, CH = CH), 6.62 (d, 2H, CH = CH), 7.09 (s, 4H, phenolic), 7.11 (d, 2H, phenolic), 7.44-7.46 (m, 4H, aromatic)

IR (cm ^-1 ): 2962, 1743, 1634, 1401, 1114

Example 7: Synthesis of 2,6-di-tert-butylphenolphthalein dimethacrylate

<Formula 10a>

2,6-ditert-butylphenolphthalein dimethacryl was subjected to the same molar ratio and process as Example 4, except that 1.89 g of 2,6-ditert-butylphenolphthalein was used instead of 3.24 g of 2-sec-phenolphthalein. The yield 2.0g (yield: 84.7%) was obtained.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 1.34 (m, 36H, CH ₃ ), 2.22 (s, 6H, CH ₃ ), 5.78 (s, 2H, CH = CH), 6.38 (s, 2H, CH = CH), 7.02 to 7.07 (m, 4H, phenolic), 7.40 to 7.44 (m, 4H, aromatic)

IR (cm ^-1 ): 2962, 1731, 1673, 1463, 1168

Example 8: Synthesis of 1-naphtholphthalein dioleate

<Formula 3a>

0.4 g of 1-naphtholphthalein and 0.16 g of triethylamine were stirred with 30 ml of methylene chloride at 5 ° C. or lower for 30 minutes. 1 ml of 70% oleoyl chloride and 5 ml of methylene chloride were added dropwise thereto using a dropping apparatus for 1 hour. Subsequently, the same process as in Example 2 was performed to obtain 0.65 g (yield: 95.7%) of the desired 1-naphtholphthalein dioleate.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 0.91 (m, 6H, CH ₃ ), 1.31 to 1.40 (m, 44H, CH ₂ ), 2.04 (m, 8H, CH ₂ (allyl)), 2.76 (t , 4H, CH ₂ ), 5.38 ~ 5.41 (m, 4H, CH = CH), 7.02 (d, 2H, naphtholic), 7.22 (, 2H, naphtholic), 7.40 (d, 1H, aromatic), 7.44 ~ 7.80 ( m, 8H, naphtholic), 7.56 (m, 1H, aromatic), 7.74 (t, 1H, aromatic), 7.97 (d, 1H, aromatic), 8.07 (d, 2H, naphtholic)

IR (cm ^-1 ): 2916, 1770, 1669, 1464, 1114

Example 9: Synthesis of Phenolphthalein Monooleate

<Formula 4b>

2.8 g of phenolphthalein, 0.85 g of triethylamine, and 40 ml of methylene chloride are added and stirred for 30 minutes. 2.8 ml of 70% oleoyl chloride was slowly added dropwise at 0 ° C. Thereafter, the same process as in Example 1 was performed to obtain 2.09 g (yield: 40.7%) of the desired phenolphthalein monooleate.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 0.90 (m, 3H, CH ₃ ), 1.27-1.37 (m, 22H, CH ₂ ), 2.04 (m, 4H, CH ₂ (allyl)), 2.58 (t , 2H, CH ₂ ), 5.37 to 5.43 (m, 2H, CH = CH), 7.06 to 7.15 (m, 8H, phenolic), 7.59 (m, 2H, aromatic), 7.74 (t, 1H, aromatic), 7.97 (d, 1H, aromatic)

IR (cm ^-1 ): 2927, 1766, 1615, 1467, 1122

Example 10 Qualitative Testing of the Identification.

To the identifier synthesized in Examples 2, 4 and 5, 1-octylpyrrolidone was added in the same amount as the labeling substance, and thereafter, a solvent of Aromatic 150 (produced by SK Corporation) was added thereto to obtain a 20% solution of the identifier. To the material synthesized in Examples 1, 3, 6 and 7, Aromatic 150 was added to prepare a 20% identification solution.

Kerosene was added to the discriminator solution to make the discriminator 10 ppm, and 50 ml were separated therefrom. To this aliquot, 5 ml of 7.5% sodium methoxide was added and analyzed by UV / VIS analyzer. The results are shown in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 λ _max (nm) 563 573 589 578 578 564 564 632 563

From the results in Table 1, it can be seen that qualitatively possible.

Example 11: Quantitative Test of Identification

An aromatic 20% solution was prepared by adding the aromatic 150 solvent to the identifiers synthesized in Examples 1, 4, and 7, respectively.

Kerosene was added to the obtained identifier solution to make the identifier 1, 5, 10, 25, 50 ppm, and 50 ml were each fractionated therefrom. To this aliquot, 5 ml of 10% sodium methoxide solution (methanol: 2-ethylhexanol = 1: 1.8) was added and analyzed by UV / VIS analyzer and the results are shown in FIGS. 1, 2 and 3, respectively.

From the results of FIGS. 1, 2, and 3, when the labeling material and the coloring agent according to the present invention are used in an oil product, it can be seen that qualitative and quantitative analysis is easy due to high solubility.

The present invention provides a method for identifying an oil product by using a lactone ester material having an unsaturated double bond as a label and using an alkanol metal salt as a colorant. The labeling substance is to introduce unsaturated double bond esters into existing phthalein derivatives, which can increase the solubility in nonpolar solvents than saturated esters. It can remove the unpleasant smell of ammonia.

Claims (7)

Lactone-based labeling material of Formula 1: <Formula 1>

In the above formula, R ₁ to R ₁₄ are each independently hydrogen, nitro group, halogen atom, carboxyl group, amino group, substituted or unsubstituted C1-30 alkyl group, substituted or unsubstituted C2-30 alkenyl group, substituted or unsubstituted A substituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 30 carbon atoms Group; R ₅ and R ₆ , R ₇ and R ₈ , R ₁₀ and R ₁₁ , or R ₁₂ and R ₁₃ may each independently combine with each other to form a fused ring; Provided that R ₉ and R ₁₄ At least one of represents a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms. The lactone-based label according to claim 1, wherein the compound of Formula 1 is a compound of Formula 2 or 3 below: <Formula 2>

In the above formula, R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , and R ₁₃ each independently represent hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, R ₉ and R ₁₄ each independently represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms, Provided that at least one of R ₉ and R ₁₄ is a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms; <Formula 3>

In the above formula, R ₉ and R ₁₄ each independently represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms, Provided that at least one of R ₉ and R ₁₄ is a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms. The lactone-based label according to claim 2, wherein the compound of Formula 2 is any one of the compounds of Formulas 4 to 10: <Formula 4>

<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

<Formula 10>

Among the above formulas, R ₉ and R ₁₄ each independently represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms, Provided that R ₉ and R ₁₄ At least one of is a substituted or unsubstituted alkenyl group having 4 to 18 carbon atoms. The lactone-based label according to claim 1, wherein each of R ₉ or R ₁₄ is independently acryl, methacryl, crotonyl, hexenoyl, octenoyl or oleoyl. Labeling an oil product using the lactone-based labeling material according to any one of claims 1 to 4; And A method of identifying an oil product, comprising the step of detecting the labeled oil product with a color developing agent in a UV / VIS region or an IR region. 6. The method of claim 5, wherein the concentration of the lactone-based labeling substance is 0.01 to 100 ppm relative to the oil product. 6. The method of claim 5, wherein the colorant is an alkanol metal salt.

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