JP2984759B2 - Novel perfluoro (2,6-dimethylmorpholinoacetyl fluoride) and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel perfluoro (2,6-dimethylmorpholinoacetyl fluoride)
And its manufacturing method. More specifically, the present invention relates to a novel perfluoro () useful as a synthetic intermediate for fluorine-containing products such as surfactants, lubricating oils, agricultural chemicals, and pharmaceuticals, and as a raw material for producing monomers for obtaining fluorine-containing plastics. The present invention relates to a 2,6-dimethylmorpholino) group-containing difluoroacetyl fluoride, and a method for efficiently producing the same using a readily available compound.

[0002]

2. Description of the Related Art Perfluorocarboxylic acid fluoride is important as a functional material, and is used as a raw material for, for example, a surfactant, a lubricating oil, a water / oil repellent, and a monomer for producing a polymer compound. Some of these perfluorocarboxylic acid fluorides are produced by an electrolytic fluorination method, but as another synthesis method, a reaction of perfluoroalkyl iodide with SO ₃ or ClSO ₃ H (French Patent No. 1,343, No. 661, U.S. Pat. No. 3,238,240) are also known. By the way, a perfluorocarboxylic acid containing a nitrogen atom as a heteroatom in a molecule is used for the above-mentioned use similar to a simple perfluorocarboxylic acid, but further has a feature that a perfluoroalkylamino group is bulky compared to the latter. Expectations as a functional material utilizing this to have it are increasing.

[0003] For example, perfluoro (morpholinoacetyl fluoride) is a known compound. After passing through several synthesis steps using this compound as a key raw material, it is converted into a fluorine-containing polymer monomer, which is further converted to tetrafluoroethylene. To create a functional polymer by copolymerization with [Polymer], Vol. 36, No. 280
7 (1995)]. That is, by utilizing the property that the perfluoromorpholino group is bulkier than the linear alkyl group, the crystallinity of the obtained polymer is reduced (that is, the amorphous property is increased), and the above-described functionality is successfully expressed. doing.

On the other hand, when a linear perfluorocarboxylic acid is used as a surfactant, it preferably has 8 or more carbon atoms. Further, when the terminal of the perfluorocarboxylic acid is branched, for example, ω, ω-bis It is known that-(trifluoromethyl) perfluorocarboxylic acid has a large interfacial lowering ability since two CF _3- effectively coordinate and act on the interface (US Pat. No. 3,525,758).
Specification). From such a point, trifluoroacetic acid having a CF ₃ — group as a side chain in the perfluorocyclic amino group and its derivative are expected to have excellent properties as a fluorine-based surfactant, Examples of the trifluoroacetic acid derivative having a group include perfluoro (pyrrolidinoacetyl fluoride), perfluoro (morpholinoacetyl fluoride), and perfluoro (piperidinoacetyl fluoride) [“Journal of
Fluorine chemistry (J. Fluorine C)
hem. 50), p. 173 (1990)
)] Is only known, so that the selection range of perfluorocarboxylic acid fluoride depending on the purpose of use was inevitably limited.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel difluoroacetyl fluoride having a perfluoro (2,6-dimethylaminomorpholino) group suitable as a synthetic intermediate for surfactants, agricultural chemicals, pharmaceuticals and the like. Another object of the present invention is to further expand the selectable range of raw materials for various products obtained by using perfluorocarboxylic acid fluoride.

[0006]

The present inventors have conducted intensive studies to develop a novel perfluorocarboxylic acid fluoride. As a result, a reactive derivative of acetic acid containing a 2,6-dimethylmorpholino group was converted to a liquid fluorine. Electrofluorination in hydrogen fluoride gives the corresponding new perfluoro (2,6
-Dimethylmorpholino) group-containing difluoroacetyl fluoride was obtained in a relatively high yield, which was found to be applicable to the same applications as conventional perfluorocarboxylic acid fluorides. I've reached the point. That is, the present invention provides the following formula (1)

[0007]

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According to the present invention, there is provided a perfluoro (2,6-dimethylmorpholinoacetyl fluoride) represented by the following formula (2):

[0009]

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Wherein X represents a halogen atom, a lower alkoxy group, an N, N-dimethylamino group, an ammonium salt or the like, and a reactive derivative of (2,6-dimethylmorpholino) acetic acid represented by the following formula: It can be produced by performing an electrolytic treatment in hydrogen fluoride.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The perfluoro (2,6) of the present invention represented by the above formula (1)
-Dimethylmorpholinoacetyl fluoride) is a novel compound at the end of the literature. In the present invention, the above formula (1)
As a raw material of perfluoro (2,6-dimethylmorpholinoacetyl fluoride) represented by the following general formula (2):
The reactive derivative of 2,6-dimethylmorpholinoacetic acid represented by the following formula is used. Examples of the reactive derivative include acid halides, lower alkyl esters, acid anhydrides, unsubstituted or N-mono- and dialkyl-substituted acid amides. Specifically, for example, 2,6-dimethylmorpholinoacetyl chloride / hydrochloride,
Preferred examples include methyl dimethylmorpholinoacetate, ethyl 2,6-dimethylmorpholinoacetate, N, N-dimethylamide 2,6-dimethylmorpholinoacetate, and ammonium 2,6-dimethylmorpholinoacetate.

Among these reactive derivatives, it is desirable to use the reactive derivative in the form of a methyl ester from the viewpoints of availability and low amount of tar-like products in the electrolytic treatment. 2,6-Dimethylmorpholinoacetic acid methyl ester can be prepared, for example, according to the method of Mofett [Journal of Organic Chemistry (J. Orn).
g. Chem. ) "Vol. 14, p. 862 (194
9 years), and by reacting 2,6-dimethylmorpholine with methyl chloroacetate, a high yield can be obtained.

In the electrolytic fluorination reaction of the present invention, an electrolytic cell conventionally used in the electrolytic fluorination reaction can be used. The reaction is carried out in liquid hydrogen fluoride. At this time, the concentration of the raw material is selected within a range of 1 to 80% by weight. It is selected in the range of 20% by weight. The current density is selected in the range of 0.01 to 10 A / dm ² , preferably 0.1 to 5 A / dm ² . If the current density is too high, the electrolysis voltage becomes too high, and a side reaction easily occurs. The electrolysis temperature is selected in the range of -20 to 50C, preferably -10 to 20C. If the temperature is too low, the electrolysis voltage tends to increase, while if it is too high, escape of hydrogen fluoride tends to occur.

This electrolytic reaction is usually carried out at normal pressure, but may be carried out under pressure if desired. When the reaction is performed under pressure, there is an advantage that the cooling of the reaction system can be eased because the boiling point of hydrogen fluoride increases. In addition, the reaction can be performed using either a continuous method or a batch method.
When the reaction is performed in a batch system, the electrolysis time for completing the reaction depends on the current density and the amount of the raw materials, but it is generally preferable to perform the reaction until the amount of electricity reaches 80 to 200% of the theoretical amount of electricity.

The perfluoro [(2,6-dimethylmorpholino) acetyl fluoride] thus obtained remains in the electrolytic cell and is separated without dissolving in liquid hydrogen fluoride to form two layers. Therefore, the lower tank (fluorinated product) can be taken out as a drain after the completion of electrolysis. The cleavage product having a low boiling point goes out of the electrolytic cell, but can be condensed and collected by a cooling trap after passing through a sodium fluoride pellet layer to remove hydrogen fluoride. Thus, the perfluoro [(2,6-dimethylmorpholino) acetyl fluoride] of the present invention obtained by fluorinating the reactive derivative of 2,6-dimethylmorpholinoacetic acid easily reacts with moisture in the air. It is a new compound that emits smoke. The compound of the present invention can be produced, for example, only by subjecting a readily available reactive derivative of 2,6-dimethylmorpholinoacetic acid to an electrolytic treatment. That it can be produced in a simple process, that it can be produced in a relatively high yield, and that perfluoro [(2,6-
Dimethylmorpholino) acetic acid], and the like.

[0016]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Example In this example, an electrolytic cell made of monel metal having a capacity of 500 ml was used, and as electrodes, seven anodes and eight cathodes made of nickel plate were alternately arranged at a distance between the electrodes of 2 mm. Used was 7.5 dm ² . 450 ml of anhydrous hydrofluoric acid was introduced into the electrolytic cell, which was preliminarily electrolyzed and purified, and then 39.5 g (0.211 mol)
l) methyl 2,6-dimethylmorpholinoacetate
Anode current density 3.3 A / dm ² , bath temperature 7 to 8 ° C., 48
Electrolysis was performed for 2 minutes (220 Ahr). The generated gas is
After removing accompanying hydrogen fluoride through a sodium fluoride tube, the solution was collected in a trap cooled to −78 ° C. in a dry ice-ethanol bath. After completion of the electrolysis, open the drain cock at the bottom of the electrolytic cell and open 42.4 g of a mixture of fluorinated products.
Was extracted. The weight of a similar product collected in the cooling trap was 16.9 g.

[0017] A small amount of molecular sieve 4A in the form of pellets is added to these fluorocarbon mixtures to remove residual traces of hydrogen fluoride, followed by gas chromatography [carrier: He, liquid phase: Fomblin YR].
25%, carrier: 60-80 mesh Chromos
orb PAW], IR, ¹⁹ F NMR, Mass, etc., showed that 30.3 g of perfluoro (2,6-dimethylmorpholinoacetyl fluoride) was produced. In addition, small amounts of perfluorodipropyl ether and perfluoro (2,6-dimethyl-N-methylmorpholine) were also obtained as cleavage products. The yield of perfluoro (2,6-dimethylmorpholinoacetyl fluoride) was 43.1%. In FIG.
4 shows analytical data of a fluorocarbon mixture (cell drain component) by gas chromatography. The physical properties of the methyl ester obtained by the reaction between perfluoro (2,6-dimethylmorpholinoacetyl fluoride) obtained as a novel compound and methanol are as follows: boiling point: 143 to 146 ° C., n
_D ²⁰ 1.3137. Because the two CF ₃ groups to perfluoroalkyl morpholine ring is substituted trans isomer (64
%) And a cis-isomer (36%). The spectroscopic data are as follows.

[0018]

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Chemical shift (ppm: CFCL ₃ standard, δ value is
TMS reference) a -80.8 (d-d) b -83.47, -91.37 (J AB) c -128.0 (m) d -85.07 (t-t) e δ3.995 ( d: doublet, J _AS: AB pattern, m: multiplet, t: t
riplet, s: singlet)

[0020]

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Chemical shift (ppm: CFCL ₃ standard, δ value is
TMS standard) a -80.52 (dd) b -77.59, -92.27 (J _AB ) c -123.3 (m) d -83.71, -87.37 (J _AB ) e δ4.006 (d: doublet, J _AS: AB pattern, m: multiplet, t: t
riplet, s: singlet)

Reference Example Conversion of perfluoro (2,6-dimethylmorpholinoacetyl fluoride) obtained in the example to the corresponding fluoro (2,6-dimethylmorpholinoacetic acid) was carried out as follows. As a raw material, a cell drain product obtained by electrolytic fluorination of (2,6-dimethylmorpholinoacetic acid) methyl ester was used as it was. First, 20 ml of ether and 39.1 g of cell drain obtained by fluorination of methyl 2,6-dimethylmorpholinoacetate are added to a 100 ml three-necked flask, and 0.5 ml of water is added every 5 minutes while stirring with a magnetic stirrer. Three times each (total 1.5 g, 0.083 mol). Stirring with a magnetic stirrer was continued, the flask was heated in an oil bath, most of the ether was drained off, and the remaining liquid was distilled under reduced pressure. The obtained perfluoro (2,6-dimethylmorpholinoacetic acid) (bp. 73 to 85 ° C./8 mmH)
The yield of g) was 26.2 g (0.0616 mol). Table 1 shows the surface tension of this potassium salt aqueous solution (25 ° C.).

[0023]

[Table 1]

[0024]

According to the present invention, easily available 2,
By electrofluorinating a reactive derivative of 6-dimethylmorpholinoacetic acid, a novel perfluoro [(2,6-dimethylmorpholino) acetyl fluoride] can be obtained in a relatively high yield. This is useful as a synthetic intermediate for fluorine-containing products such as surfactants, lubricating oils, water / oil repellents, agricultural chemicals, pharmaceuticals, etc., and as a raw material for producing monomers for obtaining fluorine-containing plastics. For example, perfluoro [(2,6-dimethylmorpholino) acetic acid] derived from the target compound of the present invention is useful as an excellent surfactant by itself, and its ability to reduce the surface tension in an aqueous solution of a potassium salt is as follows. It is comparable to industrially important sodium perfluorooctanoate and is extremely useful.

[Brief description of the drawings]

FIG. 1 shows analysis data of a fluorocarbon mixture (cell drain component) by gas chromatography.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kunio Okuhara 2-40-17 Hongo, Bunkyo-ku, Tokyo Hongo 6F, Wakai Building Examiner, Ikuharu Oya, New Refrigerant Projects Office, Research Institute for Global Environmental Technology (56) References JP-A-5-140092 (JP, A) US Pat. No. 3,525,758 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] [Claim 1] The following formula (1) (2,6-dimethylmorpholinoacetyl fluoride) represented by the formula: 2. The following formula (2): (X in the formula is a halogen atom, a lower alkoxy group, N, N
A reactive derivative of (2,6-dimethylmorpholino) acetic acid represented by the following formula (1), wherein the reactive derivative is represented by the following formula (1): Embedded image A method for producing perfluoro (2,6-dimethylmorpholinoacetyl fluoride) represented by the formula: