Method for preparing ester perfluorinated derivative by using gas chromatography

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of ester perfluorinated derivative by using a chemical reaction. This reaction represents the fluorination reaction of the parent compound as a raw, the reaction of chemical conversion of fragment of ester perfluorinated derivative to yield another ester perfluorinated derivative or the interaction reaction of carboxylic acid with alcohol under condition that at least one or reagent, i. e. carboxylic acid or alcohol, represents a perfluorinated compound wherein indicated perfluorinated derivative of ester represents a compound comprising a fragment of the formula (1):

with a boiling point 400°C, not above. The reaction time for carrying out abovementioned chemical reaction is sufficient to provide the required yield of ester perfluorinated derivative and wherein this yield of ester perfluorinated compound is determined by the gas chromatography method by using a nonpolar column. Also, invention relates to a method for pyrolysis of ester perfluorinated derivative with a boiling point 400°C, not above, to yield the dissociation product wherein this product represents a derivative of acyl fluoride or ketone and wherein pyrolysis time is sufficient to provide the required degree of conversion of ester perfluorinated derivative and wherein the indicated conversion degree of ester perfluorinated derivative is determined by gas chromatography method by using a nonpolar column. Also, invention relates to a method for analysis of ester perfluorinated derivative with a boiling point 400°C, not above, that involves analysis of ester perfluorinated derivative in a sample containing ester perfluorinated derivative by gas chromatography method by using a nonpolar column wherein ester perfluorinated derivative represents compound comprising a fragment of above given formula (1).

EFFECT: improved method of synthesis.

8 cl, 1 dwg, 2 ex

 

The technical FIELD

The present invention relates to a method for producing a fluorinated derivative of ester by gas chromatography (hereinafter referred to as GC method), the method of production of chemically modified product through chemical transformation of fluorinated derivative of ester using the GC method and the method of analysis fluorinated derivative of ester. The method which is the subject of the present invention, can be used as a method of obtaining way or chemical transformation of fluorinated derivative of ester to obtain the compound given its chemical structure, but also as a way to control the quality of fluorinated derivative of ester, etc.

The LEVEL of TECHNOLOGY

In the case when carried out obtaining fluorinated derivative of ester, or in the case where the fluorinated derivative of ester is subjected to chemical conversion to product, quantitative analysis and/or qualitative analysis (further "quantitative analysis and/or qualitative analysis" will be denoted for simplicity as analysis) fluorinated derivative of ester important to confirm the reaction, in the case of control of the conditions of receiving the product, the case of control of the quality of the obtained compound, and the like.

To this GC method was known as the method of analysis of fluorinated compounds. In addition, as the method of introduction of the sample into the GC method known way with the division, without separation, the method using the moving needle, the method cryoconcentration and the like.

In addition, there are other methods of analysis such as nuclear magnetic resonance method (NMR), high performance liquid chromatography (HPLC)method chromatography with supercritical mobile phase (SFC method), the combined method HPLC or chromatography method with supercritical mobile phase with mass spectroscopy (MS) and similar methods.

However, when using a well-known method GC in the case where the fluorinated compound is thermally unstable, the analysis can be difficult. Even in the case where the fluorinated derivative of ester is a chemically stable compound, when it is commonly accepted method GC can occur dissociation connection, and direct analysis of the connection will become very problematic.

Further, the NMR method is a generic method, however, the procedure of the analysis is complex, and because the implementation of this method does not necessarily separate, adequate quantification can be Satrughna is about, and the sensitivity can be reduced, this creates difficulties when using this method. In addition, the method of HPLC and chromatography method with supercritical mobile phase inherent in the problem, namely that the sensitivity of the method may be low.

The INVENTION

The aim of the present invention is to develop a method designed to effectively produce the product with output equal to the normal or higher than normal output, and the method of analysis of fluorinated derivative of ester, suitable for quality control specified connection by measuring with high accuracy the quantity consumed or generated fluorinated derivative of ester, and in the process effectively produce fluorinated derivative of ester and in the process of chemical transformation of fluorinated derivative of ester with getting this product through carried out with high precision analysis of fluorinated derivative of ester.

Namely, the present invention provides a method of obtaining a fluorinated derivative of ester through a chemical reaction of the raw materials, source materials, where according to this method, the chemical reaction is performed as long as the output is thoriated derived complex ester, determined by the GC method using a nonpolar column reaches a predetermined value.

The present invention also relates to a method of chemical conversion of fluorinated derivative of ester with getting this product, where according to the method of chemical conversion carried out up until the release of fluorinated derivative of ester defined by the GC method using a nonpolar column reaches a predetermined degree of conversion.

In addition, the present invention provides a method of analysis of fluorinated derivative of ester, which includes the analysis of fluorinated derivative of ester present in the sample containing fluorinated derivative of ester, the GC method using a non-polar column.

BRIEF DESCRIPTION of DRAWING

The drawing shows a chromatogram obtained by GC, where the horizontal axis represents the time in minutes for fluorinated derivative of ester obtained by the reaction of fluorination in accordance with the example analysis 1, the numeral 1 indicates the peak perforated, number 2 marked the peak of the complex perforator, and number 3 marked the peak of partially fluorinated ether complex.

The MOST PREFERRED METHOD of IMPLEMENTATION, the IMAGE IS PLACED

Fluorinated derived complex ester according to the present invention is a compound containing a fluorine atom and ester bond. The compound preferably contains the fragment shown in the following formula 1, in which the fluorine atom attached to the carbon atom located near the oxygen atom of the ester group

In formula 1 to each of the two links of the carbon atom to which is attached a fluorine atom, can be attached monovalent organic group or a monovalent atom, and these two links may form a double bond. In addition, the carbon atom to which is attached a fluorine atom, may represent the atoms included in the ring system. Preferably, in accordance with formula 1 to each of the two links of the carbon atom that is attached to the fluorine atom was attached fluorine atom or monovalent organic group, and particularly preferably, at least one connection was attached monovalent organic group. The connection, in the molecule of which contains this fragment is a compound which can undergo reaction of dissociation of the ester bonds, and represents a connection that is difficult directly to analizirovat using generally accepted methods of GC analysis, since it dissociates under the action of heat in the introduction or in a column. On the other hand, fluorinated derivative of ester preferably is a compound which has a boiling point of at most 400°C, whereas the ability to easily implement GC-analysis.

In accordance with the present invention in the process of obtaining a fluorinated derivative of ester through a chemical reaction of starting compound (raw material) use a special method of gas chromatography. The method of obtaining, for example, be a method of obtaining a fluorinated derivative of ester by the reaction of fluorination of the original connection, which may be fluorinated, how chemical transformations fragment fluorinated derivative of ester with getting this other fluorinated derivative of ester (such as the exchange of functional groups), or the mode of interaction of carboxylic acids with alcohol (provided that at least one of the reagents - carboxylic acid or alcohol - is a fluoride compound), obtaining thus fluorinated derivative of ester.

Among these methods of obtaining particularly preferable to apply the method, t is audica the subject of the present invention, in combination with the method of obtaining a fluorinated derivative of ester by the reaction of fluorination of the original connection, which may be fluorinated, because this reaction produces a lot of connections and require separation and analysis.

The fluorination reaction may represent, for example, a method of fluorination of chlorine atom with the use of potassium fluoride to replace the chlorine atom by a fluorine atom, a method of fluorination of a hydrogen atom to its replacement by fluorine atom (hereinafter indicated as direct fluorination) or the mode of interaction of fluorine with an unsaturated bond. Next, a typical example is disclosed a method of obtaining a fluorinated derivative of ester by direct fluorination.

The original connection that is used for direct fluorination, preferably represents a derived complex ester containing a hydrogen atom. In addition, direct fluorination may, for example, be a way of interacting with fluorine (F2in the liquid phase (JP-A-4-500250, WO 00/56694), a method of fluorination using cobalt or electrochemical method of fluorination, and is the preferred way of interacting with fluorine in a liquid phase. Direct fluorination of the hydrogen atom replaced by a fluorine atom and in the case when the connection has a double bond between carbon atoms, the fluorine atoms attached to the double bond with the receipt of this fluorinated derivative of ester.

The degree of introduction of fluorine in fluorinated derivative of ester (degree of introduction fluorine is the ratio of the number of fluorine atoms in the fluorinated derivative of ester to the total number of fluorine atoms in the perfluorinated compounds, formed in the result of the complete fluorination of the original connection, which may be fluorinated) is a predetermined value that depends on what the connection is scheduled to receive, a specified amount in a normal reaction set as a value equal to or greater than a specific value.

Usually pre-set value is preferably at least 80%, especially preferably at least 98% and most preferably 100%. In particular, the degree of introduction of fluorine by direct fluorination is preferably 100%.

In accordance with the present invention fluorinated derivative of ester analyze by GC method using a non-polar column. When carrying out gas chromatography using a nonpolar column can be analyzed with high precision at a convenient separation of the fluorinated derivative of ester and other soy is ineni, without dissociation fluorinated derivative of ester. In addition, when carrying out from time to time analysis of fluorinated derivative of ester in the process of obtaining a fluorinated derivative of ester can be controlled reaction conditions necessary for the effective receipt of the connection, and you can determine the completion of the reaction.

As the column used for the implementation of the GC - way, use non-polar column, in which the fluorinated derivative of ester does not dissociate. Nonpolar column preferably is a column with a layer comprising 100% poly(dimethylsiloxane) in the liquid phase or on the inner surface of the column, particularly preferably non-polar column type open tube with a coating on the walls (Wall Coated Open Tubular, i.e. column type WCOT). When using this column fluorinated derivative of ester can be analyzed essentially no dissociation fluorinated derivative of ester.

In addition, from the point of view of the quality of separation of non-polar column is preferably a capillary column, most preferably a capillary column having a length of from 5 to 120 m, particularly preferably a capillary column having a length of from 30 to 60 m, for reasons such as universal BP is me elution, the number of theoretical plates, separation and convenience. In addition, the internal diameter of the capillary column is not particularly limited and is preferably from 0.2 to 1.2 mm, the thickness of the layer of the liquid phase in the capillary column is preferably from 0.1 to 5 μm, particularly preferably from 0.25 to 1.0 μm.

Next, with the purpose of influence of the solvent or to trap non-volatile components to nonpolar side column of the input may be attached predalone using a connecting device. Predalone preferably represents predalone, having a length from 5 cm to 10 m, and is particularly preferable to use predalone length 1 m Internal diameter predalone is preferably from 0.1 mm to 1 mm, and preferably, the inner diameter of predalone was 0.25 to 0.53 mm, because they use a needle made of stainless steel or quartz glass. In addition, as predalone it is preferable to use hollow capillary with deactivated surface, made of quartz glass.

In accordance with GC-method for fluorinated derivative of ester is preferable as a method of introduction to use the method of introduction into the column without heating or method of a programmed rise in temperature in the evaporator (hereinafter kazyvaetsya as a method programmed rise in temperature in the evaporator, abbreviated as PPT-method), and the most preferred is the method of introduction into the column without heating, which is suitable for a variety of purposes and which allows to introduce the sample into the column, without exposing the sample evaporation. Method of introduction into the column without heating is a well known method and is widely used for thermally unstable compounds. In addition, in the case of using the method, the entire quantity of sample can be introduced into the column, it is less likely that the syringe or in part has evaporated selective evaporation or selective introduction into the column components of the analyzed sample, thus, this method is very suitable characteristics for quantitative analysis and is repeatable.

In addition, the particularly preferable to carry out the method of introduction without heating using an automatic injector, so that is possible to avoid subjective errors introduction of the sample, and quantitative determination can be carried out with high precision and without errors.

The input device used in the implementation of the method of introduction without heating, is commercially available, and can be mentioned, for example, devices for input, manufactured by Agilent Technologies, Perkin Elmer Inc. and Shimadzu Corporation.

The detector used according to GC-is the manual, can be used as a detector of any type. For example, there can be used a flame ionization detector, thermal conductivity detector, nitrogen-phosphorus detector, electron capture detector, flame photometric detector, photoionization detector, conductivity detector, an ionization detector surface, chemiluminescent detector, mass spectrometer, a microwave plasma-induction emission detector, an infrared spectrophotometer using a Fourier transform or a chemiluminescent detector. Among these detectors are preferred mass spectrometer and a flame ionization detector, which is most widely used for the analysis of organic compounds, such as fluorinated derivative of ester. For the analysis of fluorinated derivative of ester can be directly used method of quantitative analysis or a qualitative research method in accordance with the generally accepted analysis by gas chromatography.

According to the present invention in the process of obtaining a fluorinated derivative of ester carry out a chemical reaction as long as the output fluorinated derivative of ester defined in accordance with the above method GC, reaches a pre-set the values. The specified predefined output is optional and is usually set as a value that is equal to or higher specific output and which optionally may vary depending on the reaction conditions.

For example, if the implementation method of producing fluorinated derivative of ester by reaction of the derived complex ester containing hydrogen atoms with a fluorine compound, which is assumed to be obtained, can be synthesized with the predetermined output through the analysis of the obtained compounds having a preset degree of fluorination, the GC method. For example, in order to obtain the necessary connection with the degree of fluorination is essentially 100%, reaction conditions can be controlled by means of analysis required (target) compounds contained in the crude reaction liquid produced in the process of fluoridation, while there may be a completion of the reaction and the desired compound can be obtained with a preset output. Particularly preferably, from the point of view of application of the compounds to be used as a fluorinated derivative of ester ester compound, in which perftorirovannye essentially 100% of hydrogen atoms.

In addition, that case is e, when the direct fluorination is carried out in liquid phase, in some cases at the end of the reaction it is possible to carry out irradiation with ultraviolet rays or the introduction of benzene to increase the degree of fluorination. In this case, the duration of irradiation with ultraviolet rays or the introduction of benzene can also be controlled through the analysis of a number of fluorinated derivative of ester with a predetermined degree of introduction of fluorine. Further, by analyzing the number of fluorinated derivative of ester with a predetermined degree of introduction of fluorine after irradiation with ultraviolet rays or the introduction of benzene can be determined completion of the reaction.

In addition, according to the present invention in the process of chemical transformation of fluorinated derivative of ester with getting this product through analysis of fluorinated derivative of ester using the same technique GC, as mentioned above, the product can be carried out in such a way that the degree of transformation of fluorinated derivative of ester will comprise a predefined degree of transformation. Predefined degree of conversion can also be set as a value which is above a specific value in the ordinary case.

As a specific note is RA chemical transformation of fluorinated derivative of ester can be specified for example, the method of obtaining the derived allford or derivative of the ketone from the reaction product of dissociation, according to which the reaction of dissociation fluorinated ester bonds derived complex ester, a method of heating a fluorinated derivative of ester into a compound containing viniferin group and not containing ester bonds, as well as the way of conducting the transesterification fluorinated derivative of ester. When making such chemical transformations may be determined by the degree of transformation of fluorinated derivative of ester through the analysis of a number of fluorinated derivative of ester contained in the crude reaction liquid. In addition, by measuring from time to time, the degree of conversion in the crude reaction liquid can be efficiently carried out chemical transformations.

Additionally, in the case where GC is the method is carried out in such conditions GC-analysis for the possible implementation of the analysis of the product also can be analyzed yield the chemical transformation of fluorinated derivative of ester. For example, in the case when conducting the reaction of dissociation of fluorinated derivative of ester, h is ordinary from the reaction product of dissociation to obtain the derived allford, the only possible through analysis to further define how the output allford, and the degree of transformation of fluorinated derivative of ester, and can be controlled by the reaction conditions necessary for the effective implementation of a product, defining the end point of the chemical transformations.

The present invention also provides a method of analysis of fluorinated derivative of ester contained in the sample by gas chromatography using a nonpolar column. The method is especially suitable as a method of analysis for quality control fluorinated derivative of ester. The sample for analysis in accordance with this method may represent, for example, the crude reaction product containing fluorinated derivative of ester obtained by the chemical reaction of the raw material (the parent compound), fluorinated derivative of ester obtained when cleaning the product, the crude reaction product containing the product obtained by chemical transformation of fluorinated derivative of ester, or a product obtained by purification of the specified crude reaction product.

EXAMPLES

Hereinafter the present invention will be specifically illustrated with examples, and with avnimelech examples. However, the present invention is in no way limited to these examples.

Conditions analysis

When used as the primary column nonpolar capillary column (produced by J&W, DB-1, length 60 m, inner diameter 0.25 mm, thickness 1.0 μm) and as predalone Deaktivierung hollow capillary tube made of quartz glass (produced by GL Sciences Inc., DB-1, deactivated hollow capillary tube made of quartz glass, length 1 m, inner diameter 0,530 mm, outer diameter 0,660 mm), these speakers are connected using a connecting device for capillary columns (produced by GL Sciences Inc., Pressfit Universal Union).

The temperature of the heater support is 20°C for 5 minutes, then the temperature was raised from 20 to 270°With a speed of 10°C/min and maintained at 270°C for 5 minutes. The detector uses a flame ionization detector. To determine the structure of compounds corresponding to each peak on the chromatogram, used as a detector of the mass spectrometer. As the carrier gas using gaseous helium, the temperature of the detector is 280°C, the number of input sample is 0.03 μl, and the maximum column pressure set so that the linear velocity in the column was 25 cm/min

Sample analysis 1

In AWT the keypad with a capacity of 500 ml, made of Nickel, is placed NaF add 1,1,2-trichlorotrifluoroethane (R-113) and stirred and then cooled to -10°C. After blowing nitrogen gas for 1 hour and serve within 1 hour of gaseous fluorine, diluted to 20% with gaseous nitrogen, and is administered for 19.4 hours, the solution N(CH2)3Och(CH3)CH2OS(O)CF(CF3)O(CF2)3F in R-113.

Then, when the transmission of fluorine gas diluted to 20% with gaseous nitrogen, is injected a solution of R-113 in benzene, close the outlet valve of the autoclave, and when the pressure reaches 0.12 MPa, close the inlet valve and continue stirring for 1 hour. This operation is carried out 4 times, at this time the temperature rises from -10°C to room temperature, and then this operation is repeated 5 times at room temperature. Then within 2 hours, rinsed with gaseous nitrogen and the reaction mixture is taken by decantation to obtain the sample 1.

The chromatogram obtained by GC analysis of the sample under the above conditions analysis, shown in the drawing. Confirmed that on the chromatogram obtained by GC-analysis, the peaks of F(CF2)3OCF(CF3CF2OS(O)CF(CF3)O(CF2)3F (hereinafter referred to as complex perforator), partly the thoriated of ester F(CF 2)3OCF(CF3)COF (hereinafter referred to as perforazione) completely separate.

Next, after by means of the chromatogram obtained by GC-analysis, announced the release of complex perforator equal to 95% (the degree of introduction of fluorine is 100%), the reaction is finished. The number of perforated contained in the sample is 0.6 mol.% (amount per complex perforator). This same sample was analyzed by NMR, and the results showed the number of perforated is 0.4 mol.% (amount per complex perforator). That is, it is confirmed that the analysis is carried out essentially without dissociation of complex perforator.

Example analysis 2

The above sample 1 is heated to 145°in the presence of NaF. The crude reaction liquid in the reaction is subjected to GC analysis in the same manner described above. In the complex perforator and perforazione detected in the crude reaction liquid, but the number of complex perforator decreases during the reaction. The reaction is completed when the chromatogram obtained by GC-analysis, almost no peak is observed complex perforator. The degree of conversion of complex perforator is 98%.

In addition, the chromatogram obtained in the GC-analysis, not detected peak of F(CF2)3OCF=CF2as a product of pyrolysis of perforated. The crude reaction liquid after the reaction is additionally subjected to NMR analysis, and the results obtained are consistent with the data obtained by the GC method.

Industrial applicability

According to the production method, which is the subject of the present invention, obtaining a fluorinated derivative of ester and chemical transformation of fluorinated derivative of ester it is possible to effectively carry out analysis of the number of fluorinated derivative of ester with high accuracy. That is, the receiving may be performed in conjunction with the analysis with high accuracy degree of the reaction of fluorination or extent of pyrolysis. Furthermore, the method of analysis in accordance with the present invention can also be used as a way to control the stages of the process of obtaining that uses fluorinated derivative of ester. Additionally, the method of analysis, which is the subject of the present invention is also useful as a method of quality control of the products.

1. A method of obtaining a perfluorinated derivative of ester through a chemical reaction, where this reaction is a reaction of fluorination with wamego raw material source connection, the reaction of the chemical transformations fragment perfluorinated derived complex ester with other perfluorinated derived complex ester or the reaction of interaction of carboxylic acids with alcohol, provided that at least one of the reagents - carboxylic acid or alcohol - is a perfluorinated compound, and specified perfluorinated derived complex ester is a compound, which includes a fragment of formula 1

and has a boiling point of at most 400°Since, according to which the time mentioned chemical reaction is sufficient to output perfluorinated derived complex ester has reached a predetermined value, and the specified output perfluorinated derived complex ester determined by gas chromatography using a nonpolar column.

2. The method of receiving according to claim 1, whereby the chemical reaction of the parent compound is the reaction of fluorination of the original connection, which can be subjected to fluorination with getting this perfluorinated derived complex ester.

3. The method of receiving according to claim 2, according to which the fluorination is conducted through reaction with FPO is om in the liquid phase.

4. The method of receiving according to claim 3, whereby to implement fluoridation carry out the irradiation with ultraviolet rays or the introduction of benzene.

5. The way pyrolysis perfluorinated derived complex ester having a boiling point of at most 400°With obtaining the reaction product dissociation, and the specified product is a derivative of allford or ketone, in which the pyrolysis time is sufficient for the degree of transformation of perfluorinated derived complex ester has reached a predetermined value, and a specified degree of transformation of perfluorinated derived complex ester determined by gas chromatography using a nonpolar column.

6. The method of receiving according to claim 5, whereby the selectivity of perfluorinated derived complex ester determined by gas chromatography using a nonpolar column.

7. The way of getting any one of claims 1 to 6, according to which as a method of introduction into the gas chromatographic column used method of introduction without heating.

8. The method of analysis of perfluorinated derived complex ester having a boiling point of at most 400°With, which includes analysis of perfluorinated derived complex ester, finding the gosia in the sample, containing perfluorinated derivative of ester by gas chromatography using a nonpolar column, where a perfluorinated derived complex ester is a compound, which includes a fragment of formula 1



 

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