JP2507922B2 - Novel fluorine-containing oligomer and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel nitrogen-containing perfluorooligomers obtainable from N-trifluorovinylamine having a chain or cyclic perfluoroalkylamino group as a raw material and a process for producing the same. . More specifically, the present invention provides novel nitrogen-containing perfluorooligomers useful as synthetic intermediates for surfactants, dyes, agricultural chemicals, pharmaceuticals, etc. It relates to a method of manufacturing well.

[0002]

2. Description of the Related Art Tetrafluoroethylene or hexafluoropropylene oligomers are known as oligomers of fluorine-containing olefins [eg, Nobuo Ishikawa, Journal of Organic Synthetic Chemistry, 39, 51 (1981)]. Since these oligomers have a reactive double bond in the molecule, they are important as intermediates of useful fluorine-containing products. Using these oligomers as raw materials, the heat resistance and oxidation resistance of the perfluoroalkyl group, Lubricants utilizing low surface characteristics,
Surfactants, water repellents and oil repellents are manufactured. However, the oligomer containing a nitrogen atom in the oligomer of the fluorine-containing olefin has not been synthesized so far because it is difficult to synthesize, and in order to enhance the functionality, the functional material as disclosed in the present invention is used. There has been a demand for the emergence of new fluorine-containing oligomers that can be used.

[0003]

The object of the present invention is to provide a variety of fluorine-containing compounds, which can be produced in a high yield by a simple treatment from raw materials that are easily available under such circumstances. The purpose of the present invention is to provide a novel fluorine-containing oligomer that is useful as a synthetic intermediate of the above.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has used N-trifluorovinylamine having a chain or cyclic perfluoroalkylamino group as a raw material, When this was subjected to an oligomerization reaction in an aprotic polar solvent in the presence of a fluoride ion, it was unexpectedly found that the reaction was controlled and an olefin dimer could be selectively produced in a high yield. The present invention has been completed based on the findings.

That is, the present invention has the general formula

[0006]

[Chemical 6]

[0007]

[Chemical 7]

(In the formula, R ¹ and R ² are the same or different and each is a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms, and both are bonded directly or via an oxygen atom or a nitrogen atom. , May form a five-membered ring, a six-membered ring or a seven-membered heterocycle with the nitrogen atom to which they are bound), a dimer of perfluorovinylamine represented by According to the invention, is the general formula

[0009]

Embedded image

A perfluorovinylamine represented by the formula (wherein R ¹ and R ² have the same meanings as described above) is subjected to an oligomerization reaction in an aprotic polar solvent in the presence of a fluoride ion catalyst. Fluorine-containing oligomer (I) can be produced, and oligomer (I)
The fluorinated oligomer (II) can be produced by isomerizing the compound in a polar solvent in the presence of a fluoride ion.

The present invention will be described in more detail below. The compound represented by the general formula (I) of the present invention is a novel compound which has not been described in the literature, and R ¹ and R ² in the formula are the same or different and each is a straight chain or branched chain having 1 to 5 carbon atoms. Is a perfluoroalkyl group in which both are bonded directly or through an oxygen atom or a nitrogen atom to form a 5-membered ring, a 6-membered ring or a 7-membered heterocycle with the nitrogen atom to which they are bonded. However, preferably, bis (trifluoromethyl) amino, bis (pentafluoroethyl) amino, bis (pentafluoropropyl) amino, or perfluoropyrrolidino, perfluoropiperidino, perfluoromorpholino having a cyclic structure and the like can be mentioned. be able to. In the present invention, the perfluorovinylamine represented by the above general formula (III) is used as a raw material for producing the compound. This is, for example, the general formula

[0012]

[Chemical 9]

[In the formula, R ¹ and R ² are the same or different and each is a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms, both of which are bonded directly or via an oxygen atom or a nitrogen atom. , A 5-membered ring, a 6-membered ring or a 7-membered heterocycle may be formed together with the nitrogen atom to which both are bonded, X is a fluorine atom or OM (provided that M is
Is a monovalent alkali metal or alkaline earth metal)] and is easily obtained by heat treatment of a perfluoro (2-dialkylaminopropionyl) derivative [Japan Patent No. 1,599,192, US U.S. Pat. No. 4,782,148 (1988), U.S. Pat. No. 4,912,216 (1990)].

Examples of fluoride ion sources used in the oligomerization reaction and isomerization reaction include alkali fluorides (eg, sodium fluoride, potassium fluoride, cesium fluoride), acidic alkali fluorides (eg, sodium acid fluoride, Acidic potassium fluoride, cesium acid fluoride), fluorosulfinates (KSO ₂ F, CeSO ₂ F, etc.), quaternary ammonium fluoride and the like can be used. The amount used is 0.005 to 25% (by weight), preferably 0.1% to the aprotic polar solvent used as a solvent in the oligomerization reaction and the isomerization reaction.
It is 1-10.0% (weight).

As the aprotic polar solvent, acetonitrile, dimethylformamide, dimethylsulfoxide, sulfolane, 1-methyl-2-pyrrolidone, 1,3
Examples include, but are not limited to, dimethyl-2-imidazolidinone and hexamethylphosphoramide. The reaction temperature is 0 to 200 ° C., preferably 20.
-100 ° C. The isomerization reaction is usually carried out at 20 to 300 ° C, preferably 80 to 140 ° C. The reaction can be carried out at atmospheric pressure or under pressure.

[0016]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 A 25 ml eggplant-shaped flask with a branch equipped with a septum was equipped with a stirrer and purged with argon. Dry powdered cesium fluoride (608 mg, 4 mmol), dried dimethylformamide (DMF) (4 ml) and perfluoro (N-vinylpyrrolidine) (5.9 g, 20 mmol).
Was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into 20 ml of water, the lower layer was separated, and dried with magnesium sulfate to obtain 4.7 g of a transparent liquid. Using a semi-micro distillation device,
Distillation under atmospheric pressure was performed to obtain 3.7 g of a fraction at 140 to 147 ° C. (yield 62%). This fraction was analyzed by ¹⁹ F-NMR to find that the perfluoro (1,3-bis (pyrrolidino) -2-butene) E
It was found to be a mixture of 1: 3 ratio of body to Z body.

¹⁹ F-NMR (CDCl ₃ ) δ: E-form: −132.5 (s, 8F), −94.45 (m,
1F), -92.20 (s, 8F), -81.74.
(M, 2F), -60.76 (m, 3F) Z body: -132.95 (s, 8F), -96.36
(M, 1F), -91.84 (s, 8F), -83.3.
2 (m, 2F), -64.44 (m, 3F) MS (70 eV), m / z: E form: 590 (M ⁺ , 3.5), 571 (MF, 7.
3), 521 (M-CF 3, 12.8), 376 (3
3.1), 326 (19.6), 264 (12.2),
231 (7.3), 176 (7.8), 169 (25.
9), 150 (8.9), 131 (14.1), 100
(40.2), 93 (7.3), 69 (100) Z-form: 590 (M ⁺ , 3.7), 571 (MF, 5.
2), 521 (M-CF 3, 14.3), 376 (4
1.5), 326 (22.8) 264 (15.1), 231 (8.6), 176 (8.
2), 169 (26.4) 150 (9.8), 131 (15.1), 100 (4
1.2), 93 (7.3), 69 (100) IR (KBr): υ _max (cm ^-1 ): 1680
(Υ _{c = C} )

Example 2 A 25 ml Schlenk tube containing a stir bar was replaced with argon, and dried cesium fluoride powder (304 mg, 2 mg)
mmol), dried DMF (2 ml) and perfluoro (N-vinylmorpholine) (3.11 g, 10 mmo.
l) was added and a gas tight stopper with a Teflon seal was attached. After reacting for 20 hours at room temperature, the lower layer was separated (2.
3 g, crude yield 75%). ^{From 19} F-NMR, it was found to be the E form of perfluoro (1,3-bis (morpholino) -2-butene).

¹⁹ F-NMR (CDCl ₃ ) δ: -147.1 (d, J = 131.5 Hz, 1F) -145.4 (dm, J = 24.8 Hz, 1F) -107.8 (dd, J = 131.5Hz, 24.8H
z, 1F) -86.7--94.8 (overlapped, 16
F), -79.4 (s, 3F) MS (EI, 70 eV) m / z: 622 (M ⁺ , 0.8), 603 (M-F ⁺ , 1.8).
), 553 (12.6), 392 (8.4), 226.
(8.4), 176 (5.6), 119 (100) 114 (6.5), 100 (18.5), 97 (6.
4), 69 (43.8) IR (KBr): υ _max (cm ^-1 ): 1740
(Υ _{c = C} )

Example 3 A 25 ml Schlenk tube containing a stir bar was replaced with argon, and dried cesium fluoride powder (608 mg, 4
mmol) and dried DMF (2 ml) were put in, and a gas tight stopper with a Teflon seal was attached. Berguruoro (N, N-dimethylvinylamine) (6.99)
g, 30 mmol) was transferred by trap-to-trap and stirred at room temperature for 2 hours. The reaction solution was poured into 10 ml of water and the lower layer was separated. The extract was dried over anhydrous magnesium sulfate, filtered, and distilled under atmospheric pressure to give 5.14 g (yield 74%) of a fraction at 100-106 ° C. It was found from ¹⁹ F-NMR that this fraction was mainly composed of perfluoro (1,3-bis (N, N-dimethylamino) -1-butene) mainly in E form. Also GC-M
About 14% of perfluoro (1,3-bis (N,
It was found to contain the Z-form of N-dimethylamino) -1-butene).

¹⁹ F-NMR (CDCl ₃ ) δ: -146.2 (dm, J = 130.2 Hz, 1F),-
143.2 (m, 1F) -110.1 (ddm, J = 130.2, 20.8H
z, 1F) -78.4 (d, sepet, J = 13, 6.5 Hz,
3F) -57.4 (bs, 6F), -52.5 (m, 6F) MS (EI, 70 eV) m / z: E form: 466 (M ⁺ , 4.2), 447 (MF, 1
5.9), 397 (40.3), 359 (5.2), 3
14 (21.66), 309 (20.1), 226 (4
8.4), 221 (24.2), 176 (8.4), 1
14 (25.5), 69 (100) Z-form: 466 (M ⁺ , 0.6), 397 (9.1), 3
09 (5.1), 226 (11.3), 221 (7.
1), 114 (9.3), 69 (100) IR (KBr): υ _max (cm ^-1 ): 1745
(Υ _{c = C} )

Example 4 A 25 ml Schlenk tube containing a stir bar was replaced with argon, and dried cesium fluoride powder (608 mg, 4
mmol), dried DMF (4 ml) and the perfluoro (N, N-dimethylvinylamine) dimer obtained in Example 3 (3.73 g, 8 mmol) were added, and a gas tight stopper with a Teflon seal was installed. 110-11
It was immersed in an oil bath at 5 ° C. and stirred for 3 hours. 10 ml of reaction solution
Was poured into water and the lower layer was separated (2.75 g). 2.16 g of a 96-98 ° C. fraction was obtained by atmospheric distillation (yield 58
%). ^{By 19} F-NMR, perfluoro (1,3-bis (N, N-dimethylamino) -2-butene) E-form and Z
The body ratio was found to be 8: 1.

¹⁹ F-NMR (CDCl ₃ ) δ: E form: −100.1 (m, 1F), −82.59 (b
s, 2F), −65.21 (d, J = 18.6 Hz, 3
F), -56.63 (bs, 6F) -54.43 (m, 6F) Z-form: -96.06 (m, 1F), -81.74 (m,
2F) -61.99 (m, 3F), -57.36 (bs, 6)
F), -52.44 (m, 6F) MS (EI, 70 eV) m / z: E form: 466 (M ⁺ , 0.8), 447 (MF, 0.
5), 359 (2.7) 333 (1.1), 314 (6.0), 309 (1.
2), 271 (1.0) 264 (4.1), 226 (7.2), 176 (5.
6), 114 (8.0) 93 (1.2), 69 (100) Z-form: 466 (M ⁺ , 0.8), 447 (MF, 1.
5), 359 (2.9) 314 (5.6), 309 (1.6), 271 (1.
6), 264 (4.5) 226 (7.2), 202 (1.2), 195 (1.
3), 176 (4.8) 114 (7.7), 93 (1.4), 69 (100)

[0024]

INDUSTRIAL APPLICABILITY According to the present invention, a highly pure perfluorovinylamine dimer can be obtained in good yield by heat-treating perfluorovinylamine that is easily available in an aprotic solvent. This product is used as a synthetic intermediate for lubricants, surfactants, water repellents, paints, etc. utilizing the heat resistance, chemical resistance, light resistance, and low surface characteristics of perfluoroalkyl groups. it can. Moreover, by directly fluorinating it to a saturated body,
Alternative CFC used in the fields of foaming agents, cleaning agents, etc.
Fluorine solvent system, heat medium
^It can also be used as a medical agent such as a contrast agent by ¹⁹ F-NMR.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C07B 61/00 300 C07B 61/00 300 (56) References CHEMICAL ABSTRACT S, VOL. 122 Abstract No. 187507 (1995) CHEMICAL ABSTRACT S, VOL. 95 Abstract No. 132210 (1981) CHEMICAL ABSTRACT S, VOL. 77 Abstract number 87726 (1972)

Claims (3)

(57) [Claims] 1. A compound of the general formula Embedded image (In the formula, R ¹ and R ² are the same or different and each is a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms, and both are bonded directly or via an oxygen atom or a nitrogen atom, and both are bonded. It may form a five-membered ring, a six-membered ring or a seven-membered heterocycle with the nitrogen atom to which it is attached.
A fluorine-containing oligomer represented by. 2. A general formula: (In the formula, R ¹ and R ² are the same or different and each is a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms, and both are bonded directly or via an oxygen atom or a nitrogen atom, and both are bonded. It may form a five-membered ring, a six-membered ring or a seven-membered heterocycle with the nitrogen atom to which it is attached.
The perfluorovinylamine represented by the formula (1) is subjected to an oligomerization reaction in a polar solvent in the presence of a fluoride ion catalyst. Fluorine-containing oligomer (I) represented by (in the formula, R ¹ and R
² has the same meaning as above). 3. The general formula: wherein the fluorinated oligomer (I) is isomerized in a polar solvent in the presence of a fluoride ion. A method for producing a fluorinated oligomer (II) represented by the formula (wherein R ¹ and R ² have the same meanings as described above).