JP2967171B1 - Method for producing perfluoroalkyl group-containing alkyl iodide - Google Patents

Abstract

The present invention provides a new method for easily synthesizing a perfluoroalkyl group-containing alkyl iodide in a high yield. SOLUTION: A mixture of an acid iodide of perfluorocarboxylic acid and a terminal olefin is heated in the presence of a copper catalyst to form a perfluoroalkyl iodide by a decarbonylation reaction of the acid iodide, and at the same time the perfluoroalkyl iodide is produced. To produce a perfluoroalkyl group-containing alkyl iodide, which is characterized in that an addition reaction of the compound with a terminal olefin is carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a perfluoroalkyl group-containing alkyl iodide. The perfluoroalkyl group-containing alkyl iodide obtained according to the present invention is not only important as a synthetic intermediate for surfactants, pharmaceuticals, agricultural chemicals, liquid crystals, and fluorocarbon-based fluorocarbons, but also as a monomer for polymer synthesis. It is also important as a synthetic intermediate.

[0002]

2. Description of the Related Art Generally, the synthesis of a perfluoroalkyl group-containing alkyl iodide is carried out by a radical addition reaction of a perfluoroalkyl iodide to an olefin (Chem).
istryof Oraganic Fluorine Compounds, M. Hudli
cky, John Wiley & Sons, 2nd Ed., 1976, 420
-431). In the past, γ-rays and radical initiators were widely used as radical initiation methods.However, after that, a great deal of research has been conducted on various metal complexes and those using metals as catalysts. It extends to. Such extensive work has been done, first and foremost, in that this reaction provides the most effective means of introducing perfluoroalkyl groups. However, it is obvious that the application of this reaction is limited by the perfluoroalkyl iodide obtained. Therefore, if a new method for obtaining the same perfluoroalkyl group-containing alkyl iodide using a reagent other than perfluoroalkyl iodide could be provided, the examples of the present patent, which were difficult to synthesize with existing techniques, would be cited. Such a compound can be synthesized, and its application range is expanded. From such a background, there has been a demand for the development of a simpler method for synthesizing a perfluoroalkyl group-containing alkyl iodide having a wider range of application.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a new method for easily synthesizing a perfluoroalkyl group-containing alkyl iodide in a high yield.

[0004]

Under these circumstances, the present inventors conducted various studies in view of the above-mentioned prior art with the aim of developing a method for synthesizing a perfluoroalkyl group-containing alkyl iodide. As we proceeded, we focused on acid iodide of perfluorocarboxylic acid, and as a result of diligent efforts,
Add copper powder to a mixture of acid iodide of perfluorocarboxylic acid and terminal olefin without solvent and add heat to terminal olefin simultaneously with decarbonylation reaction by heating and stirring. It has been found that a group-containing alkyl iodide can be synthesized. The present inventors have completed the present invention based on these findings. That is, according to the present invention, a mixture of an acid iodide of a perfluorocarboxylic acid and a terminal olefin is heated in the presence of a copper catalyst to simultaneously form a perfluoroalkyl iodide by a decarbonylation reaction of the acid iodide. There is provided a method for producing a perfluoroalkyl group-containing alkyl iodide, which comprises performing an addition reaction of a perfluoroalkyl iodide to a terminal olefin.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The raw material used in the present invention is an iodide of perfluorocarboxylic acid, and its structure is not particularly limited, but the preferred one is represented by the following general formula (1) Are represented. R _f COI (1) In the above formula, R _f represents a perfluoroalkyl group which may have a perfluorocyclic substituent having a hetero atom as a ring-constituting atom. In the perfluoroalkyl group,
Its carbon number is 1-20, preferably 4-10. The perfluoroalkyl group can be a linear or cyclic saturated or unsaturated one. R _f
In a perfluorocyclic substituent having a hetero atom that may be bonded to a ring-constituting atom, the hetero atom includes
Nitrogen atom (N), oxygen atom (O) and sulfur atom (S)
And the number contained in the ring is 1-3, preferably 1 or 2. The number of ring-constituting atoms is 5-8, preferably 5-6. Examples of such a substituent include a perfluoromorpholino group, a perfluoropyrrolidino group, a perfluoropiperidino group, and the like.

The other raw material used in the present invention is a terminal olefin, and its structure is not particularly limited, but preferred examples thereof include monogaus represented by the following general formula (2). CH ₂ ＣＲCR ¹ R ² (2) In the above formula, R ¹ and R ^{2 represent} hydrogen, fluorine or an alkyl group. The alkyl group has 1 to 20 carbon atoms, preferably 4 to 10 carbon atoms.

The starting iodide of perfluorocarboxylic acid used as the starting material of the present invention is a perfluorocarboxylic acid acid fluoride (T. Abe, E. Ha
yashi, H. Fukaya, and H. Baba, J. Fluorine Che
m. 50, 173-196, 1990; T. Abe, E. Eiji, H. B
aba, and H. Fukaya, J.A. Fluorine Chem., 48,
257-279, 1990; T. Abe, E. Hayashi, H. Fukaya,
Y. Hayakawa, H. Baba, S. Ishikawa, and K.
Asahino, J. Fluorine Chem., 57, 101-111, 1992;
T. Abe, H. Fukaya, E. Hayashi, Y. Hayakaw
a, M. Nishida, and H. Baba, J. Fluorine Chem.,
66, 193-202, 1994), and can be synthesized by a halogen exchange reaction.
Fukaya, T. Matsumoto, E. Hayashi, Y. Hayakawa,
and T. Abe, J. Chem. Soc., Perkin Tans., 1, 9
15-920, 1996) and Japanese Patent Application No. 9-262842.

[0008] The copper catalyst used in the present invention is used in a form suitable for stirring and mixing, such as powder or fine flakes. In the present invention, in particular, the average particle size is 1 to 500 μm, preferably 5 to 500 μm.
It is preferable to use a powdery one having a particle size of １００100 μm.

The process of the present invention is carried out by heating a mixture of an acid iodide of perfluorocarboxylic acid and a terminal olefin in contact with a copper catalyst (for example, in the state of a mixture with a copper catalyst) to cause a decarbonylation reaction. Is done. The terminal olefin is used in an amount of 0.5 to 5 moles, preferably 0.5 to 5 moles, per mole of acid iodide of perfluorocarboxylic acid.
The proportion is 2 mol, more preferably about 1 mol. The yield of the target product is not greatly affected by the use ratio of the olefin, but in the case of a low olefin reactivity, the yield can be improved by controlling the use ratio of the olefin. . The proportion of the copper catalyst used is 0.1 to 1 mol, preferably 0.6 to 0.8 mol, per 1 mol of the acid iodide of perfluorocarboxylic acid. The reaction temperature is 80-160 ° C, preferably 1
00-160 ° C.

In the present invention, the regioselectivity of the perfluoroalkyl iodide generated by the decarbonylation reaction of acid iodide to the olefin is extremely high, and only one adduct is formed as shown in Examples described later. .
Since the present invention is free of other by-products and is a solvent-free reaction, the present invention has preferable characteristics such that purification of a perfluoroalkyl group-containing alkyl iodide as a target product can be easily performed by distillation.

The compounds represented by the general formulas (1) and (2) are given as preferred examples, and the method of the present invention is not limited to these compounds, and the method of the present invention is not limited to other perfluorocarboxylic acids. It is also applicable to acid iodides and other terminal olefins, it is possible to produce the corresponding perfluoroalkyl group-containing alkyl iodides as appropriate, and the present invention provides a method for producing a perfluorocarboxylic acid acid iodide in the presence of a copper catalyst. Can be used as a general synthesis method of a perfluoroalkyl group-containing alkyl iodide by a regioselective addition reaction to a terminal olefin accompanying the decarbonylation reaction of.

[0012]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The ¹⁹ F-NMR described in the examples was measured using deuterated chloroform as a solvent and fluoroform as an internal standard. The chemical shift value in ¹⁹ F-NMR was represented by δ ppm, where the absorption at a high magnetic field was minus than that of fluoroform. For gas chromatography (GC) measurement, a capillary column (NB-10.
25 μm 1.5 mmφ × 60 mm) and FID were used. Mass spectrometry (MS) is a quadrupole mass spectrometer with an ionization potential of 70 eV
Was measured.

Example 1 (3,3-Difluoro-1-iodo-3- (perfluoromorpholine)
No) Synthesis of propane) Copper powder in a 75-mL Hoke cylinder
Powder (450 mg, 7.09 mmol)
Morpholinoacetyl iodide (5.00 g, 11.49 mmol) and
And ethylene (283 mg, 10.08 mmol) using a vacuum line
Moved. After replacing the inside of the reaction vessel with argon, 160
Heated at 7 ° C. for 7 hours. The reaction product is distilled under reduced pressure.
And purified (4.15 g, 94.6%). ¹⁹ F-NMR: -77.55 (2F, quintet t, J = 17.2, 14.6 H
z), -86.26 (4F, s), -91.89 (4F, t J = 17.2 Hz); 1H
-NMR: 3.20 (2H, t, J = 7.2 Hz), 2.86 (2H, tt, J = 1
4.6, 7.2 Hz) .; MS: 435 (M, 17.3), 308 (M-I, 20.8),
 244 (27.7), 212 (6.8), 205 (15.5), 164 (9.7, (CF₂
CF₂) N = CF₂), 155 (8.0), 141 (15.0), 128 (5.8), 12
7 (I, 9.5), 119 (35.5), 114 (25.9, CF₂= N = CF₂), 1
00 (9.8), 97 (50.4, OC₂F₃), 78 (15.1), 77 (100),
69 (24.0), 51 (26.6), 50 (6.5), 47 (13.1, COF).

Example 2 (Synthesis of 1,1,3,3-tetrafluoro-1-iodo-3- (perfluoromorpholino) propane) Copper powder (470 mg, 7.40 mmol) was placed in a 75-mL Hoke cylinder. And then add perfluoromorpholinoacetyl iodide (5.00 g, 11.49
mmol) and vinylidene fluoride (646 mg, 10.10 mmol) were transferred using a vacuum line. After purging the inside of the reaction vessel with argon, it was heated at 160 ° C. for 7 hours. The reaction product is
Purified by gas chromatography, the 1: 1 adduct of 1,
1,3,3-tetrafluoro-1-iodo-3- (perfluoromorpholino) propane (3.12 g, yield 65.5%) (A) and 1: 2
A small amount of the adduct 1,1,3,3,5,5-hexafluoro-1-iodo-5- (perfluoromorpholino) pentane (B) was obtained (111 mg, 4.1% yield). . (A) ¹⁹ F-NMR: -41.38 (2F, quintet, J = 13.0 Hz), -7
4.14 (2F, m), -86.62 (4F, s), -92.42 (4F, t, J = 1
7.2 Hz), 1H-NMR: 3.57 (2H, quintet, J = 14.1 Hz). MS: 344 (MI, 6.6), 280 (9.4), 241 (13.1), 212 (3
2.7), 176 (29.0), 164 (16.6), 133 (100), 127 (10.
8), 119 (89.9), 114 (66.6), 113 (21.6), 100 (12.
8), 95 (6.3), 69 (49.8), 64 (25.6), 50 (7.6), 45
(10.1). (B) ¹⁹ F-NMR: -39.38 (2F, bs), -73.68 (2F, bs), -8
6.55 (4F, bs), -91.43 (2F, bs), -92.29 (4F, t, J =
16.4 Hz); ¹ H-NMR: 3.36 (2H, quintet, J = 14.8 H)
z), 2.99 (2H, quintet, J = 14.6 Hz) .MS: 408 (MI,
29.7), 304 (5.6), 280 (20.5), 241 (7.7), 197 (20.
0), 177 (32.4), 164 (11.5), 133 (95.1), 127 (15.
7), 119 (100), 114 (67.5), 113 (60.2), 100 (16.3),
97 (7.4), 95 (14.5), 69 (50.5), 64 (39.4), 51 (6.
8), 50 (7.0), 45 (12.7).

Example 3 The reaction of Example 2 was carried out using about twice the amount of vinylidene fluoride. That is, copper powder (180 mg, 2.83 mmol) was placed in a 30-mL Hoke cylinder, and perfluoromorpholinoacetyl iodide (1.66 g, 3.82 mmol) and vinylidene fluoride (821 mg, 7.20 mmol) were connected to a vacuum line. Transferred. After purging the inside of the reaction vessel with argon, it was heated at 160 ° C. for 7 hours. The reaction product is purified by gas chromatography and the 1: 1 adduct of 1,1,3,3-tetrafluoro-1-iodo-3- (perfluoromorpholino)
Propane (3.12 g, 28.8% yield) (A) and the 1,2 adduct 1,1,
3,3,5,5-hexafluoro-1-iodo-5- (perfluoromorpholino) pentane (B) was obtained (450 mg, 22% yield)
.

Example 4 (1,3,3-trifluoro-1-iodo-3- (perfluoromol
Holino) Synthesis of propane) into a 75-mL Hoke cylinder
Add copper powder (450 mg, 7.09 mmol) and add perflu
Oromorpholinoacetyl iodide (5.00 g, 11.49 mmo
l) and vinyl fluoride (469 mg, 9.97 mmol)
Transfer using After replacing the inside of the reaction vessel with argon
Was heated at 160 ° C. for 7 hours. The reaction product is
It was purified by simple distillation (3.46 g, 76.6%). ¹⁹ F-NMR: -75.99 (2F, m), -86.39 (4F, s), -92.08
(4F, t J = 17.2 Hz), -144.4 (1F, m);¹H-NMR: 7.05
(1H, ddd, J_HF = 50.4, J_HH = 9.9, 1.8 Hz) 3.52
(1H, m), 3.16 (1H, m) .; MS: 326 (M-I, 37.1), 280
(9.5), 262 (7.1), 223 (16.0), 212 (8.7), 203 (6.
7), 164 (15.1), 159 (20.5), 127 (I, 11.9), 119 (83.
8), 115 (100), 114 (62.5), 100 (15.1), 97 (5.0), 9
6 (14.0), 95 (37.2), 77 (12.6),
69 (36.8), 51 (36.8), 50
(7.8), 46 (22.1), 45 (8.
7).

Example 5 (Synthesis of 4,4-difluoro-2-iodo-4- (perfluoromorpholino) butane) A copper powder (470 mg, 7.40 mmol) was placed in a 75-mL Hoke cylinder, and further perfluoromorpholino was added. Acetyl iodide (5.00 g, 11.49 mmol) and propylene (449 mg, 10.67 mmol) were transferred using a vacuum line. After replacing the inside of the reaction vessel with argon, 160
Heated at 7 ° C. for 7 hours. The reaction product was purified by simple distillation under reduced pressure (3.12 g, 65.1%). ¹⁹ F-NMR: -74.33, -78.
35 (2F, ABquartet, J _AB = 215Hz), -86.32 (4F, s),-
91.94 (4F, t J = 17.2 Hz); ¹ H-NMR: 4.35 ( ¹ H, m) 3.
08 (1H, m), 2.86 (1H, m), 2.04 (3H, d, J = 7.2 H
z) .; MS: 322 (MI, 7.7), 258 (15.8), 212 (11.3), 155
(11.9), 127 (I, 7.0), 119 (24.8), 114 (22.7), 111
(30.3), 100 (8.1), 92 (6.4), 91 (100), 77 (9.6),
71 (9.9), 69 (11.0), 64 (6.4), 47 (88.1), 42 (5.
3), 41 (18.6).

Example 6 (Synthesis of 3,3,4,4-tetrafluoro-1-iodo-4- (perfluoromorpholino) butane) Copper powder (560 mg, 8.81 mmol) was placed in a 75-mL Hoke cylinder. And then add 3- (perfluoromorpholinopropionyl iodide (5.44 g, 11.2 g
2 mmol) and ethylene (316 mg, 11.26 mmol) were transferred using a vacuum line. After purging the inside of the reaction vessel with argon, it was heated at 160 ° C. for 7 hours. The reaction product was purified by simple distillation under reduced pressure (4.40 g, 80.8%). ¹⁹ F-NMR: -8
7.48 (4F, s), -92.47 (4F, m), -93.48 (2F, quintet,
J = 18.1 Hz), -117.5 (2F, m); ¹ H-NMR: 3.26 (2H,
t, J = 8.4 Hz), 2.70 (2H, tt, J = 17.1, 8.4 Hz) .; M
S: 485 (M, 12.4), 358 (MI, 29.6), 280 (14.5), 255
(12.5), 212 (14.6), 164 (13.7), 155 (11.0), 141 (1
4.7), 128 (10.1), 127 (I, 68.9), 119 (76.1), 114
(53.1), 100 (23.4), 97 (6.4), 78 (9.5), 77 (100), 6
9 (24.7), 65 (26.7), 59 (5.6), 57 (6.8), 51 (27.3),
50 (7.0), 47 (27.1), 44 (8.2), 40 (3.2).

Example 7 (1,1,2,2-Etrafluoro-4-iodo-1- (perfluoro
Synthesis of morpholino) decane) Teflon-coated magnetic stirring
Copper powder (63.5 m) was placed in a 10-mL branched flask with a stirrer.
g, 1 mmol), and then add 3- (perfluoromorpholine).
G) propionyl iodide (970 mg, 2.0 mmol) and 1-
Octene (1120 mg, 10 mmol) was added and cold fin was added.
A gar was attached, and the inside of the system was replaced with argon. 14 reaction vessels
It was immersed in an oil bath heated to 0 ° C. and heated and stirred for 4 hours.
The reaction solution was distilled under reduced pressure (2 mmHg) using Kuger-Rohr to obtain 748 m
g of a colorless liquid was obtained (yield: 65.7%). ¹⁹ F-NMR: -87.45 (4F, s), -92.43 (4F, t, J = 14.7
Hz), -93.70 (2F, m), -114.2, -117.3 (2F, ABquarte
t, J_AB = 266 Hz);¹H-NMR: 4.32 (1H, m), 2.81 (2
H, m), 1.70-1.90 (2H, m), 1.25-1.60 (8H, m), 0.90
(3H, t, J = 6.8 Hz); MS: 442 (M-I, 3.7), 400 (5.
9), 280 (1.1), 127 (I, 1.9), 119 (4.9), 71 (8.6), 6
9 (8.3), 56 (8.9), 55 (25.6), 47 (7.5), 44 (5.4),
43 (84.9), 42 (14.8), 41 (45.6).

[0020]

As described above in detail, the present invention relates to a method in which a mixture of acid iodide of perfluorocarboxylic acid and a terminal olefin without a solvent is heated in the presence of a copper catalyst to cause a decarbonylation reaction. The present invention relates to a method for producing a perfluoroalkyl group-containing alkyl iodide, which comprises performing a regioselective addition reaction of a perfluoroalkyl group and iodine to an olefin at the same time. It is possible to synthesize a perfluoroalkyl group-containing alkyl iodide in high yield from an acid iodide and a terminal olefin as starting materials. Perfluoroalkyl group-containing alkyl iodides are important as intermediates for synthesizing surfactants, pharmaceuticals, pesticides, liquid crystals, fluorocarbon-based fluorocarbons, and monomers for polymer synthesis.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 17/361 C07C 17/361 (72) Inventor Kunio Okuhara Hongo Wakai Building 6F, Hongo 2-40-17, Hongo, Bunkyo-ku, Tokyo Examiner, Tomohiro Fujimori, Project Director, New Refrigerants, etc., Project for Research Institute of Innovative Technology for the Environment (56) References JP-A-4-103553 (JP, A) JP-A-4-103559 (JP, A) JP-A-2-9826 ( JP, A) JP-A-7-109234 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 17/275 C07C 17/361 C07C 19/16 C07D 265/30 CA (STN ) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] A mixture of an acid iodide of a perfluorocarboxylic acid and a terminal olefin is heated in the presence of a copper catalyst to simultaneously form the perfluoroalkyl iodide by the decarbonylation reaction of the acid iodide. A method for producing a perfluoroalkyl group-containing alkyl iodide, which comprises subjecting a terminal olefin to an addition reaction of a terminal olefin. 2. The perfluorocarboxylic acid iodide may be a compound represented by the following general formula (1): R _f COI (1) wherein R _f has a perfluorocyclic substituent having a hetero atom as a ring-constituting atom. Wherein the terminal olefin is represented by the following general formula (2): CH ₂ ＣＲCR ¹ R ² (2) wherein R ¹ and R ² are fluorine, hydrogen or alkyl. The method according to claim 1, which is a compound represented by the following formula: