JPH07110837B2 - Process for producing fluorine-containing α, ω-dicarboxylic acid diester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention has a low refractive index by itself, and is a fluorine-containing α, ω-dicarboxylic acid which can be derived into a fluorine-containing polymer such as fluorine-containing polyester and polyamide. The present invention relates to a method for producing an acid diester.

[Conventional technology]

Since organic fluorine compounds have low refractive index, water and oil repellency, chemical resistance, heat resistance, etc., they are widely used in industries such as optical fiber sheath materials, fiber treatment materials, gas separation materials, photoresists, etc. There is. Fluorine-containing polymers are also used for the same purpose, but many of them contain a fluorine atom in the polymer side chain, and only a few contain a fluorine atom in the polymer main chain. The reason for this is that the required polymer raw material is an unknown compound that has not been published in the literature. For example, it is known that α, ω-dicarboxylic acid diesters can be used as raw materials for polyesters, polyamides, etc., but fluorine-containing α, ω-dicarboxylic acid diesters are compounds that have not been published in the literature.

[Problems to be Solved by the Invention]

The present invention has a simple and economical production of a novel fluorine-containing α, ω-dicarboxylic acid diester which has a low refractive index by itself and can be derived into a fluorine-containing polymer such as a fluorine-containing polyester or polyamide. It provides a method.

[Means for Solving the Problems]

The present invention has the general formula in the presence of a Group VIII transition metal catalyst and a base. (In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aralkyl group, and n represents a natural number.), And a fluorine-containing α, ω-diiodoalkane represented by the general formula R ³ OH- (III) (In the formula, R ³ represents an aralkyl group.) An alcohol represented by the general formula: (In the formula, R ¹ , R ² , R ³ and n are the same as the above.) The present invention relates to a method for producing a fluorine-containing α, ω-dicarboxylic acid diester.

The above general formula (II) used as a starting material in the present invention
The alkyl group therein is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, a methyl group, an ethyl group, a propyl group, a 3,3,3-trifluoropropyl group, a butyl group, Hexyl group, cyclohexyl group, octyl group,
A decyl group etc. can be illustrated. As the aralkyl group, an aralkyl group having 7 to 10 carbon atoms which may have a substituent, for example, a benzyl group, a pentafluorobenzyl group,
A phenethyl group etc. can be illustrated.

The fluorine-containing α, ω-diiodoalkane represented by the general formula (II) in the present invention is industrially available, but when R ¹ and R ² are the same in the formula, a transition of Group VIII group In the presence of a metal catalyst, an α, ω-diiodopolyfluoroalkane represented by the general formula I (CF ₂ ) _n I- (IV) (wherein n is the same as above) and the general formula CH ₂ = CHR ^1- (V) (In the formula, R ¹ is the same as the above.) By reacting with an olefin, it can be simply, safely and advantageously produced (see the reference example below). Α represented by the general formula (IV),
The ω-diiodopolyfluoroalkane is industrially available, and the olefin represented by the general formula (V) is also industrially available. The olefin is used in an amount of 2 equivalents or excess relative to the α, ω-diiodoperfluoroalkane represented by the general formula (IV). Examples of Group VIII transition metal catalysts that can be used include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum metals, metal salts, metal complex compounds, and organic compounds having carbon monoxide as a ligand. Metal complexes, organometallic complexes having halogen atoms as ligands, organometallic complexes having tertiary phosphines as ligands, organometallic complexes having olefins or acetylenes as ligands, and their VIII.
The group-transition metal compound supported on silica gel or alumina carrier can be used. Suitable catalysts include iron carbonyl, ruthenium carbonyl, osmium carbonyl, cobalt carbonyl, rhodium carbonyl, nickel carbonyl, iron chloride, cobalt chloride, ruthenium chloride, rhodium chloride, nickel chloride, palladium chloride, platinum chloride, dichlorobis (triphenylphosphine). ) Nickel, dichlorobis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ethane] palladium, dichloro [1,3-bis (diphenylphosphino) propane] palladium, dichloro [1,4-bis] (Diphenylphosphino) butane] palladium, dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium, dichlorobis (diphenylmethylphosphine) palladium, dichlorobis (triphenylphoh) Fin) platinum, bis (cyclooctadiene) nickel, dichloro (cyclooctadiene) palladium, tetrakis (triphenylphosphine) nickel, chlorotris (triphenylphosphine) rhodium, chlorotris (triphenylphosphine) iridium, chlorocarbonylbis (triphenyl) Phosphine)
Examples thereof include rhodium, chlorocarbonylbis (triphenylphosphine) iridium, tetrakis (triphenylphosphine) palladium and tetrakis (triphenylphosphine) platinum. The amount of the Group VIII transition metal catalyst used is α, ω − represented by the general formula (IV).
1/10000 to 1 for diiodo perfluoroalkane
The range of / 2 equivalent can be appropriately selected, but the range of 1/500 to 1/3 is preferable. If desired, amines such as pyridine, triethylamine, diethylamine and ethanolamine can be added as cocatalysts. The reaction proceeds smoothly at 0 ° C to 150 ° C. The reaction can be carried out in the absence of a solvent, but if desired, a solvent that does not participate in the reaction may be used.

Examples of the alcohol represented by the general formula (III) used in the present invention include methanol, ethanol, linear or cyclic primary or secondary propanols which may be branched, butanols, pentanols, and Hexanols, benzyl alcohol, phenethyl alcohol and the like are exemplified. The alcohol represented by the general formula (III) is usually used in excess with respect to the compound represented by the general formula (II), and may serve as a solvent.

The present invention is carried out in a carbon monoxide atmosphere and may be diluted with an inert gas that does not participate in the reaction. The reaction proceeds efficiently at a carbon monoxide partial pressure of 50 atm or less, but a high pressure may be used if desired.

The present invention has an essential condition that it is carried out in the presence of a Group VIII transition metal catalyst. Examples of the Group VIII transition metal catalyst that can be used include iron, cobalt, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum metal, metal salts, metal complex compounds, and organic compounds having carbon monoxide as a ligand. Metal complex, organometallic complex having halogen atom as ligand, organometallic complex having tertiary phosphine as ligand, organometallic complex having olefin or acetylene as ligand, and Group VIII transitions thereof A metal compound supported on silica gel or alumina carrier can be used. Suitable catalysts include iron carbonyl, ruthenium carbonyl, osmium carbonyl, cobalt carbonyl, rhodium carbonyl, nickel carbonyl, iron chloride, cobalt chloride, ruthenium chloride, rhodium chloride, nickel chloride, palladium chloride, platinum chloride,
Dichlorobis (triphenylphosphine) nickel, dichlorobis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ethane]
Palladium, dichloro [1,3-bis (diphenylphosphino) propane] palladium, dichloro [1,4-bis (diphenylphosphino) butane) palladium, dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium , Dichlorobis (diphenylmethylphosphine) palladium, dichlorobis (triphenylphosphine) platinum, bis (cyclolooctadiene) nickel, dichloro (cyclooctadiene) palladium, tetrakis (triphenylphosphine) nickel, chlorotris (triphenylphosphine) rhodium, Chlorotris (triphenylphosphine) iridium, chlorocarbonylbis (triphenylphosphine) rhodium, chlorocarbonylbis (triphenylphosphine) iridium, tetrakis (triphenyl) Sufin) palladium, tetrakis (triphenylphosphine) platinum, it can be exemplified dichloro tris (triphenylphosphine) ruthenium. The amount of the Group VIII transition metal catalyst used can be appropriately selected in the range of 1/10000 to 1/2 equivalent relative to the fluorine-containing α, ω-diiodoalkane represented by the general formula (II). A range of / 500 to 1/3 is preferred.

The present invention has an essential condition that it is performed in the presence of a base. Examples of the base include inorganics such as alkali metal or alkaline earth metal hydroxides, carbonates, fluorides and oxides, and organic bases such as triethylamine and pyridine. The amount of the base used is preferably 1 equivalent or more with respect to the compound represented by the general formula (II).

In carrying out the present invention, a solvent that does not participate in the reaction can be used. Examples of these are hexane, heptane, octane, cyclohexane, dihydrooctane and other aliphatic hydrocarbon solvents, benzene, toluene,
Aromatic hydrocarbon solvents such as xylene, acetone, chloroform, ether, tetrahydrofuran, dioxane,
A polar solvent such as t-butyl alcohol or t-amyl alcohol can be used.

If the solvent forms two liquid phases, or if the base is poorly soluble in the solvent used, a phase transfer catalyst such as a quaternary ammonium salt may be added if desired.

The reaction temperature can be appropriately selected in the temperature range of 20 to 200 ° C, but is preferably in the range of 50 to 150 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention is not limited to these Examples.

Example 1 In a 10 ml stainless steel autoclave, 1,10-diiodo-3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorodecane (0.153 g, 0.25 mmol), Co ₂ (CO) ₈ (8.5mg, 0.025mmol),
Add KF (58mg, 1mmol) and EtOH (1ml), CO (50atm)
Was encapsulated and reacted at 100 ° C. for 24 hours. Nonane (20 μl, 0.112 mmol) was added as an internal standard, and the result of quantification by gas chromatography was 4,4,5,5,6,6,7,7,8,8,9,9.
72% of diethyl dodecafluoro-1,12-dodecanedioate
It turns out that it is generating. The product was isolated and purified by silica gel column chromatography.

Anal.Calcd fo C ₁₆ H ₁₈ F ₁₂ O ₄ ． C: 38.26, H: 3.61 found C: 38.15, H: 3.54 IR (neat) 1738cm ^-1 (ν _{c = o} ) ¹ H-NMR (CDCl ₃ , TMS) δ1.26 (t, J = 7Hz, 6H) , 2.1 ~
2.9 (m, 8H), 4.18 (q, J = 7Hz, 4H). ¹⁹ F-NMR (CDCl ₃ , TMS) δ-115.2 (br, 4F), -122.4
(Br, 4F), -124.1 (br, 4F). Mass m / e (rel.int.) 502 (M ⁺ 16), 457 (100), 429 (9
9), 402 (21), 129 (26), 123 (22), 77 (24), 55 (4
8), 45 (20), 29 (93). Examples 2 to 5, except that the catalyst and the base used in the reaction were all the same as in Example 1, except that they were 4,4,5,5,6,6,7,7,8,8,9,9. -Diethyl dodecafluoro-1,12-dodecanedioate was obtained. Table 1 shows the types and amounts of the catalyst and the base used in the reaction, and the yield.

Example 6 In a 10 ml stainless steel autoclave, 1,8-diiodo-3,3,4,4,5,5,6,6-octafluorooctane (128 mg,
0.25mmol), Co ₂ (CO) ₈ (8.5mg, 0.0025mmol), KF (58m
g, 1 mmol) and EtOH (1 ml) were added, CO (50 atm) was sealed, and the mixture was reacted at 100 ° C. for 24 hours. N- as internal standard
Tetradecane (20 μl, 0.077 mmol) was added, and the result of quantification by gas chromatography was 4,4,5,5,6,6,7,7−
Diethyl octafluoro-1,10-decanedioate was produced in a yield of 64%. The product was isolated and purified by silica gel column chromatography.

Anal.Calcd for C ₁₄ H ₁₈ F ₈ O ₄ . C: 41.80, H: 4.51 found C: 41.66, H: 4.58 IR (neat) 1738cm ^-1 (ν _{c = o} ) ¹ H-NMR (CDCl ₃ , TMS) δ1.26 (t, J = 7Hz, 6H) , 2.1 ~
2.95 (m, 8H), 4.18 (q, J = 7Hz, 4H). ¹⁹ F-NMR (CDCl ₃ , TMS) δ-113.9 (br, 4F), -122.7
(Br, 4F). Mass m / e (rel.int.) 402 (M ⁺ , 6), 357 (60), 329 (3
1), 284 (5), 55 (53), 45 (16), 29 (100). Examples 7 to 11 Except for the catalyst and base used in the reaction, the reaction was carried out under the same conditions as in Example 6, and 4,4,5,5,6,6,7,7-octafluoro-1, Diethyl 10-decanedioate was obtained. Table 2 shows the types and amounts of the catalyst and the base used in the reaction, and the yield.

Example 12 In a 30 ml stainless steel autoclave, 1,6-diiodo-3,3,4,4-tetrafluorohexane (0.41 g, 1 mmol),
Co ₂ (CO) ₈ (34 mg, 0.1 mmol), KF (0.236 g, 4 mmol), and
Put EtOH (4 ml), enclose CO (50 atm), and keep at 100 ℃ for 24 hours.
Reacted for hours. After the reaction was completed, the reaction mixture was extracted with ether, washed with water, and the ether layer was dried over MgSO ₄ . The ether was distilled off under reduced pressure, and the residue was isolated and purified by silica gel column chromatography (developing solvent: chloroform). As a result, 4,4,
Diethyl 5,5-tetrafluoro-1,8-octanedioate was used.
Obtained in a yield of 233 g (77%).

Anal.Calcd for C ₁₂ H ₁₈ F ₄ O ₄ . C: 47.68, H: 6.00.found C: 47.40, H: 6.02. IR (neat) 1740cm ^-1 (ν _{c = o} ) ¹ H-NMR (CDCl ₃ , TMS) δ1.26 (t, J = 7Hz, 6H), 2.0 ~
2.8 (m, 8H), 4.18 (q, J = 7Hz, 4H). ¹⁹ F-NMR (CDCl ₃ , TMS) δ-137.7 (m, 4F). Mass m / e (rel.int.) 302 (M ⁺ 8), 257 (47), 229 (1
5), 209 (56), 55 (60), 29 (100). Example 13 Co ₂ (CO) ₈ of Example 12 was replaced with (Ph ₃ P) ₂ PdCl ₂ (70 mg, 0.1 mmol)
Example 12 except that KF was changed to Et ₃ N (0.28 ml, 2 mmol).
The reaction was carried out under the same conditions as above. As a result, diethyl 4,4,5,5-tetrafluoro-1,8-octanedioate was obtained with a yield of 86%.

Example 14 In a 50 ml stainless autoclave, 2,11-diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dotecafluorododecane (0.638 g, 1 mmol), (Ph ₃ P) ₂ PdCl ₂ (70 mg, 0.1 mmol),
KF (0.232g, 4mmol), and EtOH (4ml) were added, and CO (5
0 atm) was encapsulated and reacted at 100 ° C. for 24 hours. The reaction mixture was extracted with ether, washed with water and dried over MgSO ₄ . After the solvent was distilled off under reduced pressure, the residue was isolated and purified by silica gel column chromatography (developing solvent: chloroform). As a result, 2,11-dimethyl-4,4,5,5,6,6,7,7 0.408 g of diethyl 8,8,8,9,9-dodecafluoro-1,12-dodecanedioate
Obtained in a yield of (77%).

Anal.Calcd for C ₁₈ H ₂₂ F ₁₂ O ₄ . C: 40.77, H: 4.18.found C: 40.87, H: 4.10. IR (neat) 1740cm ^-1 (ν _{c = o} ) ¹ H-NMR (CDCl ₃ , TMS) δ1.25 (t, J = 7Hz, 6H), 1.30
(D, J = 7Hz, 6H), 1.85-3.1 (m, 6H), 4.18 (q, J = 7Hz, 4
H). ¹⁹ F-NMR (CDCl ₃ , TMS) δ-115.3 (br, 4F), -123.6
(Br, 4F), −125.7 (br, 4F). Mass m / e (rel.int.) 530 (M ⁺ 10), 485 (26), 457 (3
0), 429 (21), 91 (28), 73 (15), 47 (62), 45 (11),
29 (100). Examples 15-18 Performed in the same manner as in Example 14, 2,11-dimethyl-4,4,5,5,6,6,
Obtained diethyl 7,7,8,8,9,9-dotecafluoro-1,12-dodecanedioate. 2,11-diiodo-4,4,5,5 used in the reaction
Table 3 shows the amount of 6,6,7,7,8,8,9,9-dodecafluorododecane, the type and amount of the catalyst and the base used, the amount of the solvent, and the yield.

Example 19 2,14-Diiodo-4,4,5,5,6,6,7,7,8,8,9,9 of Example 14
-Dodecafluorododecane was added to 2,9-diiodo-4,4,5,5,
The reaction was performed under the same conditions as in Example 14 except that 6,6,7,7-octafluorodecane (0.538 g, 1 mmol) was used. As a result, diethyl 2,9-dimethyl-4,4,5,5,6,6,7,7-octafluoro-1,10-decanedioate was obtained in a yield of 0.348 g (81%).

Anal.Calcd for C ₁₆ H ₂₂ F ₈ O ₄ . C: 44.66, H: 5.15.found C: 44.38, H: 5.11.IR (neat) 1740cm ^-1 (ν _{c = o} ) ¹ H-NMR (CDCl ₃ , TMS) δ1.25 (t, J = 7Hz, 6H), 1.30
(D, J = 7Hz, 6H), 1.9 to 3.1 (m, 6H), 4.17 (q, J = 7Hz, 4
H). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ-119.9 (br, 4F), -12
6.1 (br, 4F). Mass m / e (rel.int.) 430 (M ⁺ 14), 385 (36), 357 (3
6), 269 (24), 91 (35), 47 (34), 29 (100). Examples 20-23 Performed in the same manner as in Example 19, 2,9-dimethyl-4,4,5,5,6,6,
Diethyl 7,7-octafluoro-1,10-decanedioate was obtained. The amount of 2,9-diiodo-4,4,5,5,6,6,7,7-octafluorodecane used in the reaction, the type and amount of the catalyst and the base used, the amount of the solvent, and the yield were determined. It shows in Table 4.

Reference Example 1 Table 5 shows the measured values of the refractive index of the fluorine-containing α, ω-diester obtained in the present invention. For comparison, the refractive index values of the dicarboxylic acid obtained in the present invention and the hydrocarbon diester having the same number of carbon atoms in the main chain are also shown. The refractive index was measured using an ATAGO refractometer.

Reference Example 2 I (CF ₂ ) ₄ I + CH ₂ = CH ₂ → ICH ₂ CH ₂ (CF ₂ ) ₄ CH ₂ CH ₂ I 10 ml In a stainless steel autoclave, 1,4-diiodoperfluorobutane (180 μl, 1.0 mmol), Iron pentacarbonyl (14 μl, 0.1 mmol), ethanolamine (12 μl, 0.2
mmol), ethylene (10 atm) is sealed, and 100 ° C for 3
Stir for hours. Ether was added to the reaction mixture, octane was added as a standard substance, and GLC was measured to find that 1,8-diiodo-3,3,4,4,5,5,6,6-octafluorooctane was 7
It was produced in a yield of 8%. Hydrochloric acid was added to the reaction mixture to separate the ether layer, and the ether was distilled off, followed by recrystallization from methanol to give 1,8-diiodo-3,3,4,4,5,5,
6,6-octafluorooctane was isolated and purified.

IR (KBr) 1195,1171,1112,1064,722,512cm ^-1 . ¹ H-NMR (CDCl ₃ , TMS) δ 2.1-3.0 (bm, 4H), 3.0-3.6
(Bm, 4H). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ-114.4 (m, 4F), -12
3.0 (m, 4F). Mass m / e (rel.int.) 510 (M ⁺ , 85), 383 (55), 141 (6
7), 77 (100), 65 (72), 51 (25), 47 (21), 28 (25),
27 (35). Anal.Calcd for C ₈ H ₈ F ₈ I ₂ . C: 18.84, H: 1.58. Found C: 18.76, H: 1.42. Reference Examples 3 to 17 The procedure of Reference Example 2 was repeated. Table 6 shows the amounts of 1,4-diiodoperfluorobutane and ethylene used in the reaction, the types and amounts of the catalyst and amine used, the reaction temperature, the reaction time and the yield.

Reference Example 18 I (CF ₂ ) ₆ I + CH ₂ = CH ₂ → ICH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ I 50 ml In an autoclave, 1,6-diiodoperfluorohexane (2.58 g, 4.46 mmol) iron dodeca Carbonyl (163mg,
0.32 mmol) was added and ethylene (10 atm) was enclosed, and the mixture was reacted at 80 ° C. for 5 hours. Hydrochloric acid was added to the reaction mixture, extracted with ether, and recrystallized from methanol to give 1,10-
Diiodo-3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorodecane (2.65 g) was obtained with a yield of 93%. ¹ H-NMR (CDCl ₃ , TMS) δ2.3 to 3.1 (m, 4H), 3.1 to 3.4
(M, 4H). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ-114.2 (m, 4F), -12
2.1 (m, 4F), -123.0 (m, 4F). IR (KBr) 1215,1170,1134,1064,688,512cm ^-1 . Mass m / e (rel.int.) 610 (M ⁺ , 100), 463 (24), 141 (4
6), 77 (65), 65 (43), 51 (20), 27 (19). Reference example 19 1,4-diiodoperfluorobutane (4.7 g, 10.36 mmol), Fe ₃ (CO) ₁₂ (0.2
4g, 0.48mmol) and put propylene (1240ml, 55.4mmol)
After encapsulation, the mixture was reacted at 100 ° C for 24 hours. An aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with ether. The ether layer was washed with water and dried over MgSO ₄ . After the solvent was distilled off under reduced pressure, the residue was isolated and purified by silica gel column chromatography (developing solvent: hexane). As a result, 2,9-diiodo-4,4,5,5,6,6,7,7 Octafluorodecane was obtained in a yield of 3.45 g (62%).

mp 35.0-35.5 ° C Anal.Calcd for C ₁₀ H ₁₂ F ₈ I ₂ . C: 22.33, H: 2.25.found C: 22.46, H: 2.22.IR (KBr) 1365,1268,1208,1165,1118,1032,868,715,502
cm ^-1 . ¹ H-NMR (CDCl ₃ , TMS) δ2.04 (d, J = 7Hz, 6H), 2.2〜
3.30 (m, 4H), 4.45 (tq, J = 7 and 7Hz, 2H). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ-114.2 (m, 4F), -12
4.0 (m, 4F). Mass m / e (rel.int.) 538 (M ⁺ , 2), 410 (4), 283 (2
9), 155 (12), 91 (22), 77 (11), 65 (18), 47 (10
0), 41 (25). Reference example 20 The reaction was carried out in the same manner as in Reference Example 19 except that 1,4-diiodobelufluorobutane in Reference Example 19 was changed to 1.6-diiodoverfluorohexane. As a result, 2,11-diiodo-4,4,
89% of 5,5,6,6,7,7,8,8,9,9-dodecafluorododecane
It was obtained in a yield of.

mp 53 ℃ Anal.Calcd for C ₁₂ H ₁₂ F ₁₂ I ₂ . C: 22.59, H: 1.90.found C: 22.22, H: 1.74. IR (KBr) 1455,1368,1272,1202,1170,1140,1019,689,66
0,508 cm ^-1 . ¹ H-NMR (CDCl ₃ , TMS) δ2.04 (d, J = 7Hz, 6H), 2.30 ~
3.30 (m, 4H), 4.45 (tq, J = 7 and 7Hz, 2H). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ ) δ-114.1 (m, 4F), -12
2.1 (m, 4F), -124.0 (m, 4F). Mass m / e (rel.int.) 638 (M ⁺ , 1), 384 (15), 91
(9), 65 (12), 47 (100), 43 (41).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C07C 69/65 9546-4H // C07B 61/00 300

Claims (1)

[Claims] 1. A general formula in the presence of a Group VIII transition metal catalyst and a base. (In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aralkyl group, and n represents a natural number.), And a fluorine-containing α, ω-diiodoalkane represented by the general formula R ³ OH (In the formula, R ³ represents an alkyl group or an aralkyl group.)
A general formula consisting of reacting an alcohol represented by (In the formula, R ¹ , R ² , R ³ and n are the same as above.) A method for producing a fluorine-containing α, ω-dicarboxylic acid diester.