JPH0637437B2 - Nitrogen-containing perfluoroalkyl iodide and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel nitrogen-containing perfluoroalkyl iodide and a novel method for producing the nitrogen-containing perfluoroalkyl iodide. More specifically, the present invention provides a nitrogen-containing perfluoroalkyl iodide useful as a synthetic intermediate for fluorine-containing products such as surfactants, pesticides, and pharmaceuticals, or as a material for iodine photodissociation lasers and the like. The present invention relates to a method for producing a high yield in an economically advantageous manner by using a raw material available for use as well as a novel compound obtained by the method.

BACKGROUND ART Conventionally, perfluoroalkyl iodides are known as compounds for introducing a perfluoroalkyl group because the bond between a perfluoroalkyl group and iodine is relatively weak and the bond is easily cleaved by heat or light. It is used as a synthetic raw material for fluorine-containing products such as surfactants, agricultural chemicals, and pharmaceuticals.

By the way, in a perfluoroalkyl iodide having a perfluoro (N, N-dialkylamino) group, which is one type of perfluoroalkyl iodide, since the perfluoroalkyl group has a bulky perfluoroalkylamino group, this is a building block. For example, by introducing the compound into another compound, it is possible to impart functionality such as low surface energy property and non-crystallinity. Therefore, if a nitrogen-containing perfluoroalkyl iodide is easily available as a new material, an increase in demand as a material for imparting the functionality can be expected.

As a method for producing perfluoroalkyl iodide, a mixture of N-iodinated bis (trifluoromethylamine) and perfluoropropene has been hitherto irradiated with ultraviolet rays for 10 days to obtain perfluoro (dimethylamino-2-iodopropane). Methods are known ["Journal of
The Chemical Society (J.Chem.Soc.) ", (C), 1
Vol. 971, page 3833].

However, this method is disadvantageous in that the reaction time is long, the yield is low, and the starting materials are difficult to obtain, so that the compounds to be obtained are limited. Therefore, this method is not suitable as an industrial method.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention provides various nitrogen-containing perfluoroalkyl iodides that include novel compounds useful as synthetic raw materials for various fluorine-containing compounds and new materials for iodine photodissociation laser (solar pumped laser). Using the raw materials available to
The purpose of the present invention is to provide a method for producing a product with a high yield by a simple operation.

Means for Solving the Problems As a result of intensive research to develop a novel method for producing a useful and useful perfluoroalkyl compound, the present inventors have succeeded in developing a perfluoroalkylamino group-containing perfluoroalkyl group as a raw material. It was found that a novel perfluoroalkyl iodide suitable for various applications can be obtained by heat treatment of this mixture using carboxylic acid fluoride and lithium iodide, and based on this finding, the present invention was completed. I arrived. That is, the present invention is
General formula (In the formula, R ¹ f and R ² f are the same or different from each other and are perfluoroalkyl groups having 1 to 5 carbon atoms, and they are bonded directly or via an oxygen atom or a nitrogen atom, and both are bonded to each other. A heterocycle may be formed together with the bonded nitrogen atom, and n is an integer of 1 to 3), and the nitrogen-containing perfluorocarboxylic acid fluoride and lithium iodide are heated at a temperature of 150 to 400 ° C. A general formula characterized by reacting in (Wherein R ¹ fR ² f and n have the same meanings as described above), and a method for producing a nitrogen-containing perfluoroalkyl iodide.

Hereinafter, the present invention will be described in detail.

R ¹ f and R ² f in the general formula (I) each have 1 to 1 carbon atoms.
5 are perfluoroalkyl groups, which may be the same or different from each other, and which are bonded directly or through an oxygen atom or a nitrogen atom, together with the nitrogen atom to which they are bonded. It may form a five-membered ring, a six-membered ring or a seven-membered heterocycle. That is, in the general formula (I) Examples of are:

(However, m and l are integers of 1 to 5) In the general formula (I), as, Is mentioned.

General formula (I) used as a starting compound in the method of the present invention
The nitrogen-containing perfluorocarboxylic acid fluoride of (In the formula, R ¹ and R ² are the same or different alkyl groups having 1 to 5 carbon atoms, and they are bonded directly or through an oxygen atom or a nitrogen atom, and both are bonded. A heterocyclic ring may be formed together with the nitrogen atom, and n has the same meaning as described above), and an ester or acid halide of an N, N- (dialkylamino) group-substituted carboxylic acid represented by It can be easily produced by electrolytic fluorination in hydrogen.

In the method of the present invention, the nitrogen-containing perfluorocarboxylic acid fluoride represented by the general formula (I) and lithium iodide are simply heat-treated at a temperature in the range of 150 to 400 ° C, preferably 180 to 230 ° C. Thus, the nitrogen-containing perfluoroalkyl iodide represented by the general formula (II) can be easily produced. If the temperature is lower than 150 ° C, the conversion rate is too low to be practical, and if it exceeds 400 ° C, side reactions such as decomposition occur, which is not preferable. The reaction time depends on the processing temperature and cannot be determined unconditionally,
Generally, it is about 10 seconds to 24 hours.

As the lithium iodide, either an anhydride or a hydrate can be used, but an anhydride is particularly preferable. Further, the amount used is preferably a stoichiometrically slightly excess amount with respect to the fluorocarbonyl group.

Further, this reaction can be carried out under any of reduced pressure, atmospheric pressure, and increased pressure, and any method of batch type or continuous type is also possible. In the reaction, an inert gas such as nitrogen, helium, argon, carbon dioxide, or an inert liquid such as perfluorocarbon that does not react with lithium iodide may be used as a diluent depending on the reaction mode. In this case, the dilution ratio is preferably 100 times or less.

When the reaction is carried out in a continuous system, the starting material nitrogen-containing perfluorocarboxylic acid fluoride is continuously supplied to the lithium iodide-packed layer kept at a predetermined temperature to cause the reaction, so that the corresponding content can be easily obtained. A nitrogen perfluoroalkyl iodide can be obtained. The material of the reaction vessel is not particularly limited, but usually stainless steel or hastelloy is used. In addition, the type of the packed bed is not particularly limited, such as fixed bed, moving bed, fluidized bed,
Either type can be used. According to the method of the present invention, a novel cyclic nitrogen-containing perfluoroalkyl iodide which has not been obtained by the conventional method, (Wherein X is an oxygen atom or a difluoromethylene group, m is 0 or 1, and n is an integer of 1 to 3), a cyclic nitrogen-containing perfluoroalkyl iodide represented by the following formula can be obtained. It is also an object of the present invention to provide such novel compounds. Examples of such novel compounds include perfluoro [1-pyrrolidino) ethyl iodide], perfluoro [1- (piperidino) ethyl iodide], perfluoro [1- (monofolino) ethyl iodide], perfluoro (N-methylpyrrolidine iodide), perfluoro. (N-methyl piperidine iodide),
Examples thereof include perfluoro (N-methylmorpholine iodide) and perfluoro (1-morpholino-2-iodopropane).

EFFECTS OF THE INVENTION According to the method of the present invention, novel nitrogen-containing perfluoroalkyl iodides can be obtained in an effective yield from an easily available raw material by a very simple process. It is useful as an industrial method for producing iodides.

Further, the cyclic nitrogen-containing perfluoroalkyl iodides of the general formula (III) are novel compounds that have not been published in the literature and have extremely high industrial value as raw materials for the synthesis of fluorine-containing products such as surfactants, agricultural chemicals and pharmaceuticals. Is. Further, among the compounds belonging to perfluoro [1- (cyclic alkylamino group) -substituted ethyl iodide], perfluoro [1- (piperidino) ethyl iodide] has a UV absorption maximum shifted to the long wave number side (λmax293 nm). It can be used as an iodine photodissociation laser (solar pumped laser).

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The invention is in no way limited by these examples.

Example 1 As a raw material, a product obtained by electrolytically fluorinating methyl N, N-dimethylaminoacetate was used as it was. This product contains
62.5 wt% of perfluoro (N, N-dimethylaminoacetyl fluoride) was contained.

First, the fluorocarbon mixture was added to a 75 m stainless steel reaction vessel containing 4.64 g of anhydrous lithium iodide.
39 g (containing perfluoro- (N, N-dimethylaminoacetylfluoride) 5.87 g in this) was charged, and after degassing 180
The reaction was carried out at ℃ for about 7 hours. The reaction product was first at -195 ° C.
Separated into two fractions by fractional condensation using a cold trap of -78 ° C. The compound condensed at -78 ° C was subjected to gas chromatography [carrier: He, liquid phase: 1,6-bis (1,1,12-trihydroperfluorododecyloxy)].
Hexane, carrier: 60-80 mesh Chromosorb PA
W], IR, ¹⁹ F-NMR, Mass, elemental analysis (carbon), etc. gave 4.54 g of perfluoro [(N, N-dimethylamino) iodomethane]. The yield was 74 mol% based on the consumed raw material.

The perfluoro [N, N-dimethylamino) methane iodide] is a novel compound, boiling _{^{56.5~57.0 ℃, ▲ n 20 D ▼}} 1.3
310, ▲ d is ²⁰ ₄ ▼ 2.0685, was a liquid of light purple at room temperature.

The spectroscopic data of the compound are as follows. ¹⁹ F NMR data (CF ₃ ) ₂ N CF ₂ I Chemical shift (ppm: CFCl ₃ standard) −54.6 (triplet) −19.8 (heptet) Coupling constant (Hz) − = 13.4 Mass spectrometry data m / e 310 [M−F] ⁺ 222 C ₂ F ₃ NI ⁺ 202 (CF ₃ ) ₂ NCF ₂ ⁺ Example 2 Example 1 except that the product obtained by electrolytic fluorination of methyl morpholinoacetate was used as a raw material. The reaction was performed in the same manner.

That is, 5.02 g of a fluorocarbon mixture [containing 4.22 g of perfluoro (morpholinoacetylfluoride) therein] was reacted with 2.01 g of anhydrous lithium iodide at 180 ° C. for about 6 hours and analyzed in the same manner as in Example 1. 3.62 g of perfluoro (N-methylmorpholine iodide) was obtained. The yield was 69 mol% based on the raw materials charged.

The perfluoro (N-methyl morpholine iodide) is a novel compound and has physical properties of boiling point 108.0 to 109.0 ° C, ▲ n ²⁰ _D
▼ 1.3522, was ▲ d ²⁰ ₄ ▼ 2.1211.

Example 3 A reaction was carried out in the same manner as in Example 1 except that a product obtained by electrolytically fluorinating methyl 2-piperidinopropionate was used as a raw material.

Fluorocarbon mixture 5.03 g [perfluoro in this
[2- (piperidino) propionylfluoride] 3.47 g and perfluoro [2- (methylpyrrolidino) propionylfluoride 0.68 g] and anhydrous lithium iodide 1.69 g 18
After reacting at 0 ° C. for about 6 hours and analyzed in the same manner as in Example 1, perfluoro [1- (piperidino) ethyliodide] (2.10 g) and perfluoro [1- (methylpyrrolidino) ethyliodide] (0.63) were found in the product. g) was included.
The yields of perfluoro [1- (piperidino) ethyl iodide] and perfluoro [1- (methylpyrrolidino) ethyl iodide] were each 5 based on the raw materials charged.
It was 1 mol% and 78 mol%.

The perfluoro [1- (piperidino) ethyl iodide] is a novel compound, boiling 140.0~140.5 ℃, ▲ n ²⁰ _D
▼ 1.3527, ▲ d is ²⁰ ₄ ▼ 2.1313, its UV absorption maximum indicates Ramudamax293nm, its value comparable to that of perfluoro (t-Buchiruyojido) has attracted attention as iodine Motoko dissociation laser (solar pump preparative laser) Material . The results of UV measurement of several types of nitrogen-containing perfluoroalkyl iodides are shown in the table.

Example 4 A reaction was performed in the same manner as in Example 1 except that a product obtained by electrolytically fluorinating methyl 3- (diethylamino) propionate was used as a raw material.

That is, 4.92 g of a fluorocarbon mixture [containing 3.17 g of perfluoro [3-diethylamino) propionylfluoride] therein] and 1.68 g of anhydrous lithium iodide
When reacted at 180 ° C. for about 18 hours, 4.55 g of a clear purple reaction mixture was obtained. When this product was washed with an aqueous solution of sodium thiosulfate (about 5 wt%), it became a colorless and transparent liquid (4.38 g), but gradually became a pale cherry color. When analyzed in the same manner as in Example 1, it contained 2.75 g of perfluoro [2- (diethylamino) ethyliodide].
The yield was 72 mol%).

The compound is a novel compound, and its physical property value is boiling point 125.5-12.
The temperature was 6.5 ° C, ▲ n ²⁰ _D ▼ 1.3344, and ▲ d ²⁰ ₄ ▼ 2.0914.

Example 5 A reaction was carried out in the same manner as in Example 1 except that a product obtained by electrolytically fluorinating 3-morpholinoisobutyric acid methyl was used as a raw material.

That is, 5.00 g of fluorocarbon mixture (wherein perfluoro (3-morpholinoisobutyryl fluoride 3.
89 g] and 1.57 g of anhydrous lithium iodide at 6 ° C at 6 ° C.
The reaction was carried out for half an hour, and the obtained liquid was washed with an aqueous sodium thiosulfate solution for purification. When this product was analyzed in the same manner as in Example 1, it was found that perfluoro (1-morpholino-2-
3.50 g (yield: 76 mol%) of iodopropane was contained.

The compounds are novel compounds, boiling point from 144.0 to 145.0 ° C., ▲ n ²⁰
_D ▼ 1.3482, had physical properties ▲ d ²⁰ ₄ ▼ 2.1357.

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Claims (2)

[Claims] 1. (X in the formula is an oxygen atom or a difluoromethylene group, m is 0 or 1, and n is an integer of 1 to 3) A cyclic nitrogen-containing perfluoroalkyl iodide. 2. General formula (In the formula, R ¹ f and R ² f are the same or different from each other and are perfluoroalkyl groups having 1 to 5 carbon atoms, and they are bonded directly or via an oxygen atom or a nitrogen atom, and both are bonded to each other. A heterocycle may be formed together with the bonded nitrogen atom, and n is an integer of 1 to 3), and a nitrogen-containing perfluorocarboxylic acid fluoride and lithium iodide are represented at a temperature of 150 to 400 ° C. General formula characterized by reacting (Wherein R ¹ f, R ² f and n have the same meaning as described above), and a method for producing a nitrogen-containing perfluoroalkyl iodide.