JP3409316B2 - Novel perfluoro {1,4-bis [2- (fluorocarbonyl) -n-propyl] piperazine} and process for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel perfluorodicarboxylic acid fluoride and a method for producing the same. More specifically, the present invention is useful as a raw material for producing monomers such as synthetic intermediates for fluorine-containing products such as surfactants, lubricating oils, water / oil repellents, agricultural chemicals and pharmaceuticals, and fluoroplastics. , A novel perfluoro {1,4-bis [2- (fluorocarbonyl) -n-propyl] piperazine}, and a method for efficiently producing this compound using a readily available compound.

[0002]

2. Description of the Related Art Conventionally, perfluorodicarboxylic acid fluoride has been a famous compound as a raw material for surfactants, lubricating oils, water / oil repellents, agricultural chemicals, pharmaceuticals, high molecular weight monomers, etc. It is manufactured by the chemical method.

By the way, perfluorodicarboxylic acid fluoride having a perfluoropiperazino group in the molecule is
Although it is a compound useful as a synthetic intermediate which can give various useful fluorine-containing products having the perfluoropiperazino group, it has hitherto been slightly perfluoro (piperazine-N,
N′-di-β-propionic acid fluoride) (US Pat. No. 3,471,484), perfluoro (piperazine-N, N′-di-α-propionic acid fluoride) (Japanese Patent No. 1451067), perfluoro. Only (piperazine-N, N'-diacetylfluoride) (Japanese Patent No. 2946045) is known, and the selection range of perfluorocarboxylic acid fluoride is limited according to various purposes of use. I was not spared.

[0004]

Under these circumstances, the object of the present invention is to provide a novel perfluoro {1 which is useful as a synthetic intermediate or a raw material for various fluorine-containing products having a perfluoropiperazino group. Another object of the present invention is to provide a method for efficiently producing 4-bis [2- (fluorocarbonyl) -n-propyl] piperazine}, and a compound from which this compound is easily available, by electrolytic fluorination.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventor can easily synthesize 1,4-bis (1,4-bis) bis (meth) methacrylate as a raw material by an addition reaction with anhydrous piperazine. By using [2- (methoxycarbonyl) -n-propyl] piperazine and electrolytically fluorinating this compound in liquid hydrogen fluoride, it was found that the intended purpose can be achieved, and further research has been conducted.
The present invention has been completed. That is, the present invention provides the following formula (1)

[0006]

[Chemical 4]

The present invention provides perfluoro {1,4-bis [2- (fluorocarbonyl) -n-propyl] piperazine}. The present invention also provides a compound of the following formula (2)

[0008]

[Chemical 5]

(X in the formula represents a halogen atom, a lower alkoxy group, an N, N-dimethylamino group, or an ammonium salt), and is represented by piperazine-N, N'-di-β-is.
The present invention provides a method for producing a reactive derivative of o-butyric acid by subjecting it to electrolytic treatment in liquid hydrogen fluoride.

The compounds of the present invention are preferably of the formula

[0011]

[Chemical 6]

By subjecting 1,4-bis [2- (methoxycarbonyl) -n-propyl] piperazine represented by the formula (1) to electrolytic treatment in liquid hydrogen fluoride, a difunctional perfluorocarboxylic acid fluoride can be obtained comparatively. It can be manufactured in good yield.

In the present invention, the starting material piperazine
As the reactive derivative of N, N′-di-β-iso-butyric acid, for example, acid halogenide (chloride, fluoride), methyl ester, ethyl ester, N, N-dimethylamide and the like are used. Synthesis of these raw materials (ie,
Obtained means) is easily carried out by the reaction of commercially available piperazine with methacrylic acid ester (methyl ester, ethyl ester), and the obtained adduct is used as it is or by further derivatization with acid halogenide or amide. Be done. For example, 1,4-bis [2- (methoxycarbonyl) -n-propyl] piperazine most preferably used as the fluorinated raw material of the compound of the present invention is commercially available raw material anhydrous piperazine, methyl methacrylate and methanol in a solvent. By heating, it is synthesized by a one-step reaction (Michael addition reaction).

In the electrolytic fluorination reaction of the present invention, an electrolytic cell conventionally used in the electrolytic fluorination reaction can be used. Further, the reaction is carried out in liquid hydrogen fluoride, in which case the concentration of the raw material is selected in the range of 1 to 80% by weight, and if this concentration is high, a tar-like substance is likely to be formed, so it is preferable. Is selected in the range of 3 to 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 this current density is too high, the electrolysis power will be too high and side reactions will easily occur. The electrolysis temperature is selected in the range of -20 to 50 ° C, preferably -10 to 20 ° C. If this temperature is too low, the electrolysis voltage tends to increase, while if it is too high, hydrogen fluoride tends to escape.

This electrolysis reaction is usually carried out at normal pressure, but it may be carried out under pressure if desired. When it is carried out under pressure, the boiling point of hydrogen fluoride increases, so that the cooling of the reaction system can be moderated. Further, the reaction may be either a continuous method or a batch method, but when the reaction is carried out in a batch method, the electrolysis time for completing the reaction depends on the current density and the amount of the raw material, but in general, It is preferable to carry out the reaction for a time period such that the quantity of electricity becomes 80 to 200% of the theoretical quantity of electricity.

Since these electrolytic fluorination conditions differ depending on the type of raw material used, it is desirable to appropriately select them in consideration of the yield of target product and current efficiency. In addition, it is desirable to stir the electrolytic solution during the reaction in order to efficiently perform electrolytic fluorination and to improve the yield of the target product.For that purpose, mechanical forced stirring and stirring by the introduction of an inert gas are required. And the like can be used.

The perfluoro {1,4-bis [2- (fluorocarbonyl) -n-propyl] piperazine} thus obtained remains in the electrolytic cell and does not dissolve in liquid hydrogen fluoride. Since the two layers are formed separately, the liquid hydrogen fluoride can be easily taken out after the liquid hydrogen fluoride is recovered after the electrolysis is completed. Further, the cleavage product having a low boiling point goes out of the electrolytic cell, but after passing through the sodium fluoride pellet layer to remove hydrogen fluoride, it can be condensed and collected by a cooling trap.

Thus, the perfluoro {1,4-bis [2- (fluorocarbonyl) of the present invention obtained by electrolytic fluorination of 1,4-bis [2- (methoxycarbonyl) -n-propyl] piperazine -N-propyl] piperazine} is a colorless and transparent wax-like compound at room temperature, and has a melting point of 58 to 61 ° C and a boiling point of 192.0 to 192.5 ° C.
Is a novel compound not yet published in the literature.

The novel compound of the present invention is a synthetic intermediate for producing a useful fluorine-containing compound having a perfluoropiperazino group, a reaction route for the synthetic intermediate to reach a useful compound, and the synthetic intermediate. A synthetic route for producing a useful plastic monomer from the body will be specifically described below. 1) An example of producing a useful compound from the synthetic intermediate of the present invention is shown below.

[0020]

[Chemical 7]

The compound obtained in the above 1) can be converted into an alcohol which is a raw material of a monomer or a water / oil repellent, as shown in a synthesis example described later. 2) An example of producing useful plastic monomers and polymers from the synthetic intermediate of the present invention is shown below.

[0022]

[Chemical 8]

A fluoropolymer can be synthesized by polymerizing the monomer obtained in the above 2). These are important as water-repellent and chemical-resistant polymers.

[0024]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example In this example, an electrolytic cell made of monel metal was used, and as an electrode, seven nickel plate-made anodes and eight cathodes were alternately arranged at a distance between electrodes of 2 mm. The value used was 7.5 dm ² .

1,4-Bis [2-
(Methoxycarbonyl) -n-propyl] piperazine 3
A solution prepared by dissolving 9.9 g and adjusting the whole amount to 450 ml was used as an electrolytic solution and electrolyzed at 229 Ahr at 5.5 to 5.6 V. The produced gas was passed through a sodium fluoride tube to remove the accompanying hydrogen fluoride, and then was dried at -78 in a dry ice-ethanol bath.
It was collected in a trap cooled to ℃. After the electrolysis was completed, the fluorocarbon mixture was distilled off anhydrous hydrofluoric acid from the electrolytic cell, and then while heating the electrolytic cell, a wax-like compound was collected from the inside of the cell at room temperature of 51.0 g.

These fluorocarbon mixtures were subjected to gas chromatography [carrier: He, liquid phase: From]
blin H 15%, carrier: 60-80 mesh Chromosope PAW]], IR, ¹⁹ F-NMR, Mass, etc., showed that it was perfluoro [3- (4-n-propylpiperazinyl) -iso-butyric acid fluoride] 6 .
With 9 g (yield 8.3%), perfluoro {1,4
-Bis [2- (fluorocarbonyl) -n-propyl]
Piperazine} was obtained in an amount of 31.5 g (yield: 36.5%).

Perfluoro {1,4-bis [2- (fluorocarbonyl) -n-propyl] piperazine} obtained as a novel compound of a fluorine-containing bifunctional perfluorocarboxylic acid has a melting point of 58 to 61 ° C. and a boiling point of 192. 0-19
It is a waxy compound at room temperature with 2.5 ° C. and its spectroscopic data are as follows.

[0028]

[Chemical 9]

¹⁹ F-NMR (CCl ₃ F standard) (1) 33.9 ppm (double line) J ((1)-(3)) = 17.1 Hz (2) -73.3 (3) -177 .3 (4) -82.9, -86.7 J _AB = 248 Hz (5) -92.7 Synthesis Example 1) A specific process for synthesizing the above-mentioned starting materials is shown below.

[0030]

[Chemical 10]

2) The reaction of the synthetic intermediate of the present invention with anhydrous lithium iodide gives the corresponding diiodide compound. This compound is further represented by the following reaction formula:
It can be converted into an alcohol which is a raw material of a monomer or a water and oil repellent.

[0032]

[Chemical 11]

[0033]

INDUSTRIAL APPLICABILITY According to the present invention, 1) readily available perfluoro (piperazine-N, N'-di-α-butyric acid)
The novel derivative of perfluoro {1,4-bis [2- (fluorocarbonyl) -n-propyl] piperazine} can be obtained in relatively high yield by electrolytically fluorinating the reactive derivative of 1) 2) Commercially available raw material 1,4-bis [2- that can be easily synthesized by a one-step reaction (Michael addition reaction)
By electrolytically fluorinating (methoxycarbonyl) -n-propyl] piperazine, novel perfluoro {1,4-bis [2- (fluorocarbonyl)] is obtained in relatively good yield.
-N-propyl] piperazine} is obtained. 3) This compound is used as a synthetic intermediate for fluorine-containing products such as surfactants, lubricating oils, water / oil repellents, agricultural chemicals and pharmaceuticals, and also to obtain fluorine-containing plastics. It is a compound useful as a raw material for producing a monomer.

[Brief description of drawings]

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

─────────────────────────────────────────────────── ─── Continuation of front page (73) Patent holder 000002004 Showa Denko Co., Ltd. 1-13-9 Shibadaimon, Minato-ku, Tokyo (73) Patent holder 000002200 Central Glass Co., Ltd. 5253 Oki Obe, Ube-shi, Yamaguchi ( 73) Patent holder 000002853 Daikin Industries, Ltd. 2-4-12 Nakazaki Nishi, Kita-ku, Osaka City, Osaka Prefecture Umeda Center Building (73) Patent holder 000003034 Toagosei Co., Ltd. 1-14-1 Nishi-Shimbashi, Minato-ku, Tokyo ( 73) Patent holder 000174851 Mitsui DuPont Fluorochemical Co., Ltd. 1-5-18 Sarugaku-cho, Chiyoda-ku, Tokyo (72) Inventor Takashi Abe 7-6, Oshizawadai, Kasugai-shi, Aichi Prefecture (72) Inventor, Baba Koshi Tokyo 2-40-70 Hongo, Bunkyo-ku, Tokyo 6th floor, Hongo Wakai Bldg. Research Institute for Global Environmental Industrial Technology New refrigerants -Object chamber (56) Reference Patent Sho 62-22772 (JP, A) patent 2946045 (JP, B2) US Patent 3471484 (US, A) (58 ) investigated the field (Int.Cl. ^7, DB name) C07D 241/04 C25B 3/08 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. The following formula (1): Perfluoro {1,4-bis [2- (fluorocarbonyl) -n-propyl] piperazine} represented by 2. The following formula (2): (X in the formula is a halogen atom, a lower alkoxy group, N,
N-dimethylamino group, which represents an ammonium salt), a reactive derivative of piperazine-N, N′-di-β-iso-butyric acid represented by the formula (1) is electrolyzed in liquid hydrogen fluoride. The following formula (1) A method for producing perfluoro {1,4-bis [2- (fluorocarbonyl) -n-propyl] piperazine} represented by