JP2936195B2 - Perfluorocarboxylic acid ester and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention provides a method for synthesizing a perfluorocarboxylic acid ester by directly adding a perfluorocarboxylic acid to an olefin. More specifically, the present invention provides a method for regioselectively synthesizing a perfluorocarboxylic ester, which is an addition reaction product, by mixing an olefin and a perfluorocarboxylic acid and performing a heat reaction without a solvent. . The obtained perfluorocarboxylic acid ester has uses as a detergent, a water repellent, a lubricant, or a liquid crystal.

[0002]

BACKGROUND OF THE INVENTION Esters of perfluorocarboxylic acid are
A carboxylic acid is converted into an acid halide in the same manner as a hydrocarbon-based carboxylic acid ester, and is then synthesized by reacting with a corresponding alcohol, or is synthesized by condensing an acid and an alcohol with a dehydrating agent or the like. I have. There are few reports on the synthesis of esters by the addition of perfluorocarboxylic acids to olefins. Research has been limited [PE
Peterson and G. Allen, J. Org. Chem. 1961, 27, 2290
-2291; PE Peterson and G. Allen, J. Am. Chem. S
oc. 1963, 85, 3608-3613]. Synthetically significant addition of perfluorocarboxylic acid to olefins is reported to be trifluoroacetic acid added to isobutylene to give trifluoroacetic acid t-butyl ester in 75% yield. [MM Joullie, J. Am. Chem. S
oc. 1955, 77, 6662], it has been reported that, for terminal olefins, multiple products are formed due to internal shifts produced by hydride shifts and proton elimination [PE Peterson, J. Am. . Chem. Soc. 1960, 8
2, 5834-5837; PE Peterson and G. Allen, J. Or
g. Chem. 1962, 27, 1505-1509]. In the addition reaction between isobutylene and trifluoroacetic acid, the intermediate of the reaction is a carbocation of tertiary carbon, which is particularly stable;
Furthermore, the elimination reaction of trifluoroacetic acid from the tert-butyl ester of trifluoroacetic acid, which is the reverse reaction of the addition reaction, is a very special reaction system in which only the starting olefin, isobutylene, is generated. Extension to olefins can be difficult. fact,
In the PE Peterson et al. Document cited above, the addition of trifluoroacetic acid to the terminal olefin is known to have the effect of inhibiting isomer formation in the presence of a 25% excess of the sodium salt of trifluoroacetic acid. When the addition reaction to 1-hexene is performed in
Hexyl esters and 3-hexyl esters are reported to be formed in a 3: 1 ratio. On the other hand, the addition of acetic acid, which is a hydrocarbon-based carboxylic acid, to 1-octene proceeds when montmorillonite substituted with Cr3 is used as a catalyst, and an adduct mixture consisting of a plurality of products is also obtained. [JA Ballantine, M. Davies, H. Purnell,
M. Rayanakorn, JM Thomas, and KJ Williams,
J. Chem. Soc. Chem. Commun. 1981, 8-9].

[0003] As described above, the addition reaction of trifluoroacetic acid to an olefin gives a single addition product with a limited substrate of isobutylene, but the terminal olefin gives a mixture of several kinds of additions. However, the synthesis of perfluorocarboxylic acid esters is currently performed by the above-mentioned conventional methods, but each has problems. For example, a conversion reaction of a carboxylic acid into an acid halide requires the use of a highly toxic reagent, and a dehydration condensation reaction using an acid catalyst has a problem in yield. Against this background, there has been a demand for a simpler method for synthesizing perfluorocarboxylic acid esters.

[0004]

Under these circumstances, the present inventors have been conducting various studies with the aim of developing a method for synthesizing perfluorocarboxylic acid esters in view of the above prior art. Focusing on the addition reaction of perfluorocarboxylic acid to olefin, as a result of diligent efforts, a mixture of perfluorocarboxylic acid and olefin without solvent is heated and stirred at a relatively high temperature of about 120 to 160 ° C. It has been found that a perfluorocarboxylic acid alkyl ester as a regioselective addition product can be obtained in good yield. The present inventors have completed the present invention based on these findings. An object of the present invention is to provide a simpler method for synthesizing a perfluorocarboxylic acid ester.

[0005]

The present invention for solving the above-mentioned problems is characterized in that a mixture of a perfluorocarboxylic acid and an olefin is heated and reacted at a relatively high temperature without a solvent. This is a method for synthesizing a perfluorocarboxylic acid ester by a regioselective addition reaction to an olefin. Normally, it can be considered that the reaction at a lower temperature improves the selectivity of the reaction. It was difficult to predict from the report. The present invention is the above-mentioned compound having a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms, which may be substituted with a substituent having a perfluorocyclic structure containing a hetero atom such as oxygen or nitrogen. A preferred embodiment of the above-mentioned method for producing a perfluorocarboxylic acid ester from an olefin, wherein the olefin is a linear or branched olefin having 1 to 20 carbon atoms which may have a functional group such as a carboxyl group. It is assumed that.

[0006]

Next, the present invention will be described in more detail. As described above, the present invention relates to a general synthesis method for producing a perfluorocarboxylic acid ester by reacting a perfluorocarboxylic acid and an olefin with heating without a solvent. Here, the perfluorocarboxylic acid is not particularly limited, and an appropriate compound can be used.
The compound represented by the following general formula (1) is exemplified. As the olefin, a terminal olefin represented by the following general formula (2) is exemplified as a typical one. However, the method of the present invention is not limited to these compounds, and the same applies to other compounds. It is possible to apply.

Next, the method of the present invention will be described with reference to typical compounds. That is, the present invention provides the following general formula (1) to give a preferred example.

[0008]

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(In the formula, Rf is a straight chain having 1 to 20 carbon atoms which may be substituted by a substituent having a perfluorocyclic structure such as perfluoromorpholino or perfluoropyrrolidino, which contains a heteroatom such as oxygen or nitrogen. And a chain or branched perfluoroalkyl group, wherein a perfluoroalkyl group is a hydrocarbon group in which all hydrogen atoms have been replaced by fluorine atoms) and a compound represented by the following general formula (2):

[0010]

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Wherein R ¹ is hydrogen or a lower alkyl group having 1 to 5 carbon atoms, and R ² is a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted with an alkoxycarbonyl group. The present invention provides a general synthesis method for producing a perfluorocarboxylic acid ester as an addition product by reacting a mixture of olefins represented by the following formulas with no solvent:

In the present invention, there are many commercially available perfluorocarboxylic acids as starting materials.
Those which are not commercially available were obtained by electrolytic fluorination of the corresponding hydrocarbon-based carboxylate esters by methods known in the literature (T. Abe, E. Hayashi, H. Fukaya, and H. Ba
ba, J. Fluorine Chem. 50, 173-196, 1990; T. Abe, E.
Eiji, H. Baba, and H. Fukaya, J. 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. F
ukaya, E. Hayashi, Y. Hayakawa, M. Nishida, and H.
Baba, J. Fluorine Chem., 66, 193-202, 1994). The reaction was carried out on the other starting material, olefin, which was commercially available. The reaction can be carried out by using 1-6 equivalents of olefin per 1 equivalent of perfluorocarboxylic acid, but preferably by using 3-4 equivalents to add and produce expensive perfluorocarboxylic acid without waste. Can be converted to something. However, the relative price of the perfluorocarboxylic acid and the olefin varies depending on the case, so that when the olefin is relatively high, the reaction does not decrease so much even if the reaction is carried out in almost the same amount. Although the optimum temperature varies depending on the substrate used, it is generally preferable to carry out the reaction at 80 to 180 ° C, preferably at 120 to 160 ° C. In the reaction method of the present invention, by using such a relatively high temperature, a result having less side reaction products and good selectivity can be obtained. Purification of the addition product can be easily performed by simple distillation because there are no side reaction products. The compounds described in the above general formula are given as preferred examples, and the method of the present invention is not limited to these compounds, and the corresponding perfluorocarboxylic acid ester can be produced from other perfluorocarboxylic acids and olefins. The present invention can be used as a general synthesis method for producing perfluorocarboxylic acid esters from perfluorocarboxylic acids and olefins.

[0013]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Example 1 2-octyl perfluoromorpholinoacetic acid perfluoromorpholinoacetic acid (535 mg, 1.65 m
mol) and 1-octene (672 mg, 6 mmol) were placed in a 20-mL branched flask, charged with a Teflon-coated magnetic stirrer, and fitted with a Dimroth condenser. After the inside of the reaction vessel was replaced with argon, the vessel was placed in an oil bath heated to 150 ° C., and heated and stirred for 1 hour. Reaction liquid ¹⁹
F-NMR indicated a conversion of 79% and a selectivity of the product of 100%. The reaction solution was placed under reduced pressure (2 mmH
g) with a Kuhger-Rohr and a fraction up to 120 ° C. (F1,619 mg) and a fraction up to 150 ° C. (F
2,187 mg). The F2 fraction was almost pure 2-octyl perfluoromorpholinoacetate (yield 2
6%; the yield considering the conversion is 33%). F1
Was a mixture, mostly product, but containing a small amount of starting acid and 1-octene. ¹⁹ F-NMR: -92.01, -91.12 (AB quartet m, J = 205 Hz,
4F), -86.91, -85.22 (AB quartet m, J = 224 Hz, 2
F), -85.69 (AB quartet d overlapped, J = 18.9Hz, 4
F), ¹ H-NMR: 5.10 (sextet, J = 6.4 Hz, 1 H), 1.69
(m, 1H), 1.60 (m, 1H), 1.33 (d, J = 6.4 Hz, 3H),
1.20-1.36 (m overlapped, 8H), 0.88 (t, J = 7.1 Hz,
3H), ¹³ C ｛ ¹ H, ¹⁹ F｝ -NMR: 158.2, 113.0 (overlappe
d), 110.0,77.23, 35.36, 31.60, 28.89, 24.88, 22.4
9, 19.19, 13.96, IR: 1784 (ν _{C = 0} ), MS (EI, 70eV): 2
81 (1.1), 280 (CF ₂ N (CF ₂ CF ₂ ) ₂₀ , 17.8), 164 (6.0),
145 (1.4), 142 (1.4), 119 (24.1), 114 (28.7), 112
(27.1), 100 (7.3), 97 (9.9), 95 (1.9), 85 (3.0), 8
4 (30.9), 83 (51.1), 82 (15.9), 81 (1.6), 78 (1.
3), 72 (3.3), 71 (70.0), 70 (73.4), 69 (37.0), 68
(6.1), 67 (4.8), 58 (4.1), 57 (96.0), 56 (55.8), 5
5 (68.8), 54 (4.2), 53 (3.9), 51 (1.5), 50 (2.7), 4
7 (1.2), 45 (2.0), 44 (6.6), 43 (100), 42 (44.3),
41 (90.5)

Example 2 Perfluoro (3-pyrrolidinopropionic acid) 2-octyl Perfluoro (3-pyrrolidinopropionic acid) (540)
mg, 1.50 mmol) and 1-octene (672 m
g, 6 mmol) was placed in a 20 mL branched flask, a Teflon-coated magnetic stirrer was placed therein, and a Dimroth condenser was attached. After the atmosphere in the reaction vessel was replaced with argon, the vessel was placed in an oil bath heated to 150 ° C., and heated and stirred for 5 hours. According to ¹⁹ F-NMR of the reaction solution, the conversion was 9
At 8%, the product selectivity was found to be 96%. The reaction solution was distilled with a Kuhger-Rohr under reduced pressure (2 mmHg) to obtain a fraction (446 mg) up to 140 ° C. ¹⁹
According to F-NMR and ¹ H-NMR, it was almost pure perfluoro (3-pyrrolidinopropionic acid) 2-octyl (yield 79% in consideration of the conversion). ¹⁹ F-NMR: -133 (s, 4F), -119.2 (quintet, J = 10.3 H
z, 2F), -93.36 (quintet, J = 12.0 Hz, 2F), -90.62
(quintet, J = 11.1 Hz, 4F), ¹ H-NMR: 5.14 (sextet,
J = 6.4 Hz, 1H), 1.70 (m, 1H), 1.60 (m 1H), 1.34
(t, J = 6.3 Hz, 3H), 1.28-1.35 (m, 8H), 0.89 (t, J
= 7.2 Hz, 3H), ¹³ C ｛ ¹ H, ¹⁹ F｝ -NMR: 158.0, 113.4,
113.0, 107.8, 107.1, 77.24, 35.44, 31.62, 28.90, 2
4.98, 22.52, 19.42, 13.98, IR (KBr): 1778 (
ν _{C = O} ), MS (EI, 70eV): 314 (CF ₂ CF ₂ N (CF ₂ CF ₂ ) ₂ , 4.
6), 264 (8.3), 214 (1.9), 176 (7.2), 164 (1.4), 1
63 (1.9), 145 (1.4), 131 (1.9), 119 (18.4), 114 (5.
0), 113 (5.0), 112 (29.8), 100 (9.4), 97 (9.4), 93
(1.1), 85 (3.2), 84 (34.8), 83 (57.1), 82 (17.3),
81 (2.0), 76 (1.0), 72 (3.5), 71 (68.8), 70 (80.
9), 69 (46.2), 68 (6.9), 67 (5.6), 58 (4.6), 57 (8
8.1), 56 (58.8), 55 (82.8), 53 (4.3), 50 (1.3), 47
(16.1), 45 (3.0), 44 (6.7), 43 (100), 42 (48.5), 4
1 (95.6)

Example 3 Perfluoro (3-pyrrolidinopropionic acid) 2-hexyl Perfluoro (3-pyrrolidinopropionic acid) (540
mg, 1.50 mmol) and 1-hexene (673 m
g, 8 mmol) was taken in a 20 mL Pyrex ampoule, a Teflon-coated magnetic stirrer was put therein, and then sealed under an argon atmosphere. 150 unpooled
It was placed in an oil bath heated to ℃ and heated and stirred for 5 hours. According to ¹⁹ F-NMR and GC of the reaction solution, the conversion was 9
At 2%, the product selectivity was found to be 96%. The reaction solution was subjected to Kuhger-Rohr distillation under reduced pressure (2 mmHg) to obtain a fraction at 100 ° C (510 mg). ¹⁹ F
-NMR indicated perfluoro (3-pyrrolidinopropionic acid) 2-hexyl with a purity of 78%. The raw material perfluoro (3-pyrrolidinopropionic acid) is 17
And 5% of a compound whose structure was not determined but was considered to be perfluoro (3-pyrrolidinopropionic acid) 3-hexyl. The yield considering the conversion was 67%. ¹⁹ F-NMR: -133 (s, 4F), -119.2 (quintet, J = 9.5 H
z, 2F), -93.36 (quintet, J = 12.0 Hz, 2F), -90.93
(tt, J = 12.0, 9.5 Hz, 4F), ¹ H-NMR: 5.14 (sextet,
J = 6.5 Hz, 1H), 1.71 (m, 1H), 1.61 (m, 1H), 1.34
(d, J = 6.3 Hz, 3H), 1.29-1.37 (m, 4H), 0.91 (t, J
= 6.6 Hz, 3H), ¹³ C ( ¹ H, ¹⁹ F｝ -NMR: 158.1, 113.4,
113.1, 107.8, 107.1, 77.30, 35.14, 27.17, 22.35, 1
9.42, 13.81, IR: 1778 (ν _{C = O} ), MS (EI, 70 eV): 38
6 (1.6), 366 (0.7), 314 (4.2), 264 (5.9), 214 (1.
3), 176 (4.2), 164 (1.1), 163 (2.4), 145 (1.1), 13
1 (1.4), 119 (16.4), 114 (3.7), 100 (7.6), 85 (50.
1), 84 (38.7), 83 (2.0), 69 (41.2), 57 (15.7), 56
(36.6), 55 (34.5), 47 (18.1), 44 (6.9), 43 (100), 4
2 (32.0), 41 (43.1)

Example 4 Perfluoro (3-pyrrolidinopropionic acid) cyclohexyl Perfluoro (3-pyrrolidinopropionic acid) (539)
mg, 1.50 mmol) and 1-hexene (493 m
g, 6 mmol) was taken in a 20 mL Pyrex ampoule, a Teflon-coated magnetic stirrer was put therein, and then sealed under an argon atmosphere. 150 unpooled
It was placed in an oil bath heated to ℃ and heated and stirred for 5 hours. According to ¹⁹ F-NMR and GC of the reaction solution, the conversion was 9%.
At 2%, the product selectivity was found to be 96%. The reaction solution was subjected to Kuhger-Rohr under reduced pressure (2 mmHg).
To obtain a fraction at 100 ° C. (485 mg). ¹⁹
According to F-NMR, the perfluoro (3-
Cyclohexyl pyrrolidinopropionate).
The remaining 21% was the starting material perfluoro (3-pyrrolidinopropionic acid). The yield considering the conversion is 73
%Met. ¹⁹ F-NMR: -133.0 (s, 4F), -119.3 (quintet, J = 9.9
Hz, 2F), -93.48 (quintet, J = 12.0 Hz, 2F), -90.63
(tt, J = 12.0, 9.9 Hz, 4F), ¹ H-NMR: 5.04 (tt, J =
8.7, 3.9 Hz, 1H), 1.91 (m, 2H), 1.78 (m, 2H), 1.5
7 (m, 3H), 1.40 (m, 3H), ¹³ C ｛ ¹ H, ¹⁹ F｝ -NMR: 157.
8, 113.4, 113.1, 107.8, 107.1, 78.29, 30.95, 25.07,
23.26, IR: 1776 (ν _{C = O} ), MS (EI, 70eV): 314 (0.
8), 264 (5.5), 214 (1.7), 176 (3.1), 164 (1.0), 14
5 (1.6), 131 (1.5), 119 (13.1), 114 (4.1), 100 (7.
8), 97 (1.0), 84 (5.1), 83 (83.8), 82 (100), 81 (1
1.9), 69 (11.9), 68 (5.0), 67 (82.1), 56 (8.1), 55
(56.4), 54 (36.2), 53 (5.2), 43 (7.6), 42 (6.9),
41 (45.1)

Example 5 Methyl 3-perfluoro (3-pyrrolidinopropionyloxy) propionate Perfluoro (3-pyrrolidinopropionic acid) (400
mg, 1.11 mmol) and methyl acrylate (383
(6 mg, 6 mmol) was taken in a 20 mL Pyrex ampoule, a Teflon-coated magnetic stirrer was put therein, and then sealed under an argon atmosphere. 15 unpools
It was placed in an oil bath heated to 0 ° C., heated and stirred for 16 hours. According to ¹⁹ F-NMR of the reaction solution, the conversion was 45%.
The product selectivity was found to be 65%. The reaction solution was distilled with a Kuhger-Rohr under reduced pressure (2 mmHg) to obtain a fraction (219 mg) at 120 ° C. ¹⁹ F-N
By MR, 65% of starting material perfluoro (3-pyrrolidinopropionic acid) and 35% of methyl 2-perfluoro (3-pyrrolidinopropionyloxy) propionate were obtained.
Turned out to be a mixture of The yield considering the conversion is 40%.
Met. ¹⁹ F-NMR: -132.9 (s, 4F), -119.9 (quintet, J = 9.9
Hz, 2F), -93.78 (quintet, J = 13.0 Hz, 2F), -90.66
(tt, J = 13.0, 9.9 Hz, 4F), ¹ H-NMR: 4.65 (t, J =
6.3 Hz, 2H), 3.74 (s, 3H), 2.80 (t, J = 6.3 Hz, 2
H), ¹³ C ｛ ¹ H, ¹⁹ F｝ -NMR: 170.4, 159.6, 113.3, 113.
0, 107.8, 107.2, 63.54, 52.33, 33.09, IR: 1786, 173
2 (ν _{C = O} ), MS (EI, 70eV): 341 (1.7), 264 (6.4), 2
14 (1.3), 207 (1.0), 191 (1.1), 176 (2.7), 159 (1.
2), 145 (1.8), 131 (2.6), 121 (1.4), 119 (12.1), 11
4 (2.5), 103 (7.9), 100 (10.3), 97 (1.3), 87 (33.
6), 85 (4.8), 73 (4.7), 71 (5.5), 69 (14.3), 59 (8
9.4), 55 (100), 45 (12.8), 44 (27.1), 43 (31.4), 4
2 (8.0), 41 (10.7),

EXAMPLE 6 Perfluoro (2-morpholinopropionic acid) 2-octyl Perfluoro (2-morpholinopropionic acid) (510)
mg, 1.36 mmol) and 1-octene (672 m
g, 6 mmol) was placed in a 20 mL branched flask, a Teflon-coated magnetic stirrer was placed therein, and a Dimroth condenser was attached. After the inside of the reaction vessel was replaced with argon, the vessel was placed in an oil bath heated to 110 ° C., and heated and stirred for 48 hours. According to ¹⁹ F-NMR of the reaction solution, the conversion rate,
Both product selectivities were found to be 100%. The reaction solution was distilled on a Kuhger-Rohr under reduced pressure (2 mmHg),
A fraction up to 150 ° C. (374 mg) was obtained. The product contained two sets of enantiomeric mixtures in a 1: 1 ratio. The combined yield of the four diastereomers was 56%. ¹⁹ F-NMR: -140.1 (m, 1F), -88.27, -83.68 (AB quarte
t, J = 148 Hz, overlapped 8F), -75.87 (m, 3F); -14
2.5 (m, 1F), -93.47, -87.66 (AB quartet, J = 202 H
z, 4F), -93.14, -87.26 (AB quartet, J = 202 Hz, 4
F), -76.71 (m, 3F), ¹ H-NMR: 5.13 (m, 1H), 1.70 (m,
! H), 1.60 (m, 1H), 1.33 (d, J = 6.3 Hz, 3H), 1.28
-1.35 (m, ovelapped, 8H), 0.89 (t, J = 7.2 Hz, 3
H), ¹³ C ｛ ¹ H, ¹⁹ F｝ -NMR: 158.47, 158.43 (ν _{C = O} ),
119.12 (CF ₃ ), 113.02, 110.71 (O (CF ₂ CF ₂ ) ₂ N), 94.4
7, 94.40 (CF ₃ C * -N), 78.02, 77.91 (OC *), 35.28, 3
5.27 (OC * -CH ₂ ), 31.62 (t), 28.90 (t), 24.79 (t),
22.50 (t), 18.97, 18.93 (q, CH ₃ -C *), 13.97 (q), I
R: 1778 (ν _{C = O} ), MS (EI, 70eV): (first peak): 330
(9.6), 214 (1.8), 192 (1.3), 164 (13.9), 145 (1.
7), 128 (1.2), 119 (40.1), 114 (4.3), 113 (5.1), 11
2 (36.5), 100 (7.6), 97 (10.5), 84 (29.4), 83 (47.
1), 82 (13.4), 71 (64.7), 70 (76.2), 69 (36.7), 68
(6.5), 57 (97.1), 56 (57.0), 55 (64.7), 44 (8.6),
43 (100), 42 (41.1), 41 (76.9); (second peak): 330
(7.4), 214 (1.3), 164 (13.7), 145 (1.7), 128 (1.
2), 119 (40.2), 114 (4.8), 113 (5.1), 112 (38.3), 1
00 (7.3), 97 (10.8), 84 (28.7), 83 (47.7), 82 (13.
8), 71 (65.0), 70 (76.1), 69 (37.2), 68 (6.6), 57
(100), 56 (59.8), 55 (65.1), 44 (8.0), 43 (98.9),
42 (40.6), 41 (72.9)

Example 7 Perfluoro (octanoic acid) 2-octyl perfluorooctanoic acid (621 mg, 1.50 mmol)
l) and 1-octene (673 mg, 6 mmol) in 10
The mixture was placed in a mL-volume branched flask, charged with a Teflon-coated magnetic stirrer, and fitted with a Dimroth condenser. After the inside of the reaction vessel was replaced with argon, the vessel was placed in an oil bath heated to 140 ° C., and heated and stirred for 16 hours. The reaction solution was distilled using a Kuhger-Rohr under reduced pressure (10 mmHg) to obtain a 150 ° C. fraction (477 mg). ¹⁹
From F-NMR and other spectra, it was found to be an addition product, perfluoro (octanoic acid) 2-octyl (yield: 660%). ¹⁹ F-NMR: 126.62 (m, 2F), 123.14 (overlapped, 4F),
122.52 (brs, 2F), 122.08 (brs, 2F), 119.04 (t, J = 1
0.7Hz, 2F), 81.27 (t, J = 10.3Hz, 3F) ¹ H-NMR: 5.14 (sextet, J = 6.6Hz, 1H), 1.70 (m, 1H),
1.61 (m, 1H), 1.34 (d, J = 6.3Hz, 3H), 1.28-1.35 (ov
erlapped, m, 7H), 0.88 (t, J = 6.4Hz, 3H) ¹³ C ｛ ¹ H, ¹⁹ F｝ -NMR: 158.19 (ν _{C = O} ), 117.52, 111.
14 (overlapped), 110.89, 108.87, 108.43, 77.29, 3
5.67, 31.75, 29.03, 25.06, 22.57, 19.45, 13.87, I
R: 1778 (ν _{C = O} ), MS (EI, 70eV): 441 (0.6), 413 (2.
5), 369 (1.7), 281 (1.1), 231 (1.0), 219 (1.3), 11
3 (4.9), 112 (31.0), 100 (4.9), 97 (8.5), 84 (27.
3), 83 (47.3), 82 (13.1), 71 (55.8), 70 (77.2), 69
(63.2), 68 (6.5), 67 (5.1), 58 (4.4), 57 (84.7), 5
6 (63.5), 55 (85.6), 53 (4.0), 44 (9.5), 43 (100),
42 (49.9), 41 (88.5), 40 (5.5)

Example 8 Perfluoro (butanoic acid) 2-octyl perfluorobutanoic acid (642 mg, 3 mmol) and 1
-10 mL of octene (1350 mg, 12 mmol)
Into a Teflon-coated magnetic stirrer.
A stirrer was put in, and a Dimroth condenser was attached. Inside the reaction vessel
Was replaced with argon, and then heated to 150 ° C.
And heated and stirred for 5 hours. Reaction solution¹⁹F-NM
Depending on R, the conversion is 81.5% and the selectivity of the product is 9
It turned out to be 4.5%. The reaction solution was placed under reduced pressure (10 mmH
g) by distillation using Kuhger-Rohr to give 110
A fraction at 310C (310 mg) was obtained.¹⁹F-NMR and its
From other spectra, the addition product perfluoro (porcine
Acid) 2-octyl (yield 32%).¹⁹ F-NMR: 127.5 (s, 2F), 120.0 (quartet, J = 8.1Hz, 2
F), 81.3 (t, J = 8.6Hz, 3F),¹H-NMR: 5.14 (sextet, J =
6.4 Hz, 1H), 1.70 (m, 1H), 1.59 (m, 1H), 1.34 (d, J
= 6.4Hz, 3H), 1.28-1.35 (overlapped, m, 8H), 0.89
(t, J = 6.3Hz, 3H) ¹³ C ｛¹H,¹⁹F｝ -NMR: 158.07 (ν_{C = O}), 117.75 (C
F_Three), 108.54, 107.88, 77.23, 35.61, 31.69, 28.97, 2
5.01, 22.54, 19.44, 13.88, IR: 1778 (ν_{C = O}), MS (E
I, 70eV): 241 (2.2), 213 (3.4), 197 (2.4), 169 (1
6.5), 119 (1.8), 113 (2.4), 112 (17.9), 97 (6.8), 8
4 (27.4), 83 (42.8), 82 (12.8), 71 (36.2), 70 (77.
8), 69 (53.0), 68 (7.3), 67 (5.4), 57 (60.8), 56
(64.5), 55 (83.1), 54 (5.0), 53 (4.5), 47 (4.3), 44
 (9.5), 43 (98.2), 42 (53.4), 41 (100), 40 (6.7)

Example 9 Perfluoro (propionic acid) 2-octyl perfluoropropionic acid (492 mg, 3 mmol)
And 1-octene (1350 mg, 12 mmol) in 10
The sample was taken in a mL-volume Pyrex unpool, and a Teflon-coated magnetic stirrer was put thereinto, followed by sealing under an argon atmosphere. The unpool was placed in an oil bath heated to 150 ° C., and heated and stirred for 5 hours. ¹⁹ F-NMR of the reaction solution
Gives a conversion of 72.4% and a product selectivity of 9
It turned out to be 3.3%. The reaction solution was placed under reduced pressure (10 mmH
In g), distillation was performed using a Kuhger-Rohr to obtain a fraction at 110 ° C (691 mg). ^{From 19} F-NMR and other spectra, it was found to be an addition product, perfluoro (propionate) 2-octyl (yield: 83%). ¹⁹ F-NMR: 122.32 (s, 2F), 83.35 (s, 3F), ¹ H-NMR:
5.14 (sextet, J = 6.4Hz, 1H), 1.70 (m, 1H), 1.60 (m,
1H), 1.34 (d, J = 6.3Hz, 3H), 1.28-1.35 (overlapped,
m, 8H), 0.89 (t, J = 6.6Hz, 3H), ¹³ C ｛ ¹ H, ¹⁹ F｝ -NM
R: 158.2 (ν _{C = O} O), 118.1 (CF ₃ ), 106.3, 77.0, 3
5.7, 31.7, 29.0, 25.1, 22.6, 19.5, 13.9, IR: 1778
(ν _{C = O} ), MS (EI, 70eV): 191 (3.9), 163 (4.2), 147
(4.0), 119 (21.6), 112 (12.2), 97 (5.5), 84 (23.8),
83 (41.1), 82 (10.4), 71 (30.4), 70 (73.7), 69 (3
6.0), 68 (6.4), 67 (5.2), 57 (49.8), 56 (61.4), 55
(82.6), 47 (5.4), 44 (7.3), 43 (86), 42 (47), 41
(100)

Example 10 2-octyl trifluoroacetate (342 mg, 3 mmol) and 1-octene (1350 mg, 12 mmol) were placed in a 10 mL Pyrex unpool, and a Teflon-coated magnetic stirrer was added. And sealed under an argon atmosphere. Place the unpool in an oil bath heated to 150 ° C.
Heated and stirred for hours. ¹⁹ F-NMR of the reaction solution revealed that the conversion was 70.8% and the selectivity for the product was 93.2%. The reaction solution was Kuhg under reduced pressure (10 mmHg).
er-Rohr, and the fraction at 110 ° C. (691 m
g) was obtained. ^The product was found to be 2-octyl trifluoroacetate as an addition product from ¹⁹ F-NMR and other spectra (yield: 46%). ¹⁹ F-NMR: -75.93, ¹ H-NMR: 5.10 (sextet, J = 6.4Hz, 1
H), 1.70 (m, 1H), 1.61 (m, 1H), 1.34 (d, J = 6.4Hz, 3
H), 1.28-1.35 (overlapped, m, 8H), 0.89 (t, J = 5.1H
z, 3H), ¹³ C ｛ ¹ H, ¹⁹ F｝ -NMR: 157.36 (ν _{C = O} ), 114.
94 (CF ₃ ), 76.68, 35.67, 31.74, 29.02, 25.13, 22.58,
19.53, 13.91, IR: 1782 (ν _{C = O} ), MS (EI, 70eV): 1
41 (6.9), 113 (7.8), 112 (10.1), 97 (8.0), 84 (26.
6), 83 (43.2), 82 (11.2), 71 (24.3), 70 (80.1), 69
(56.8), 68 (6.4), 67 (5.3), 57 (46.0), 56 (65.4),
55 (85.3), 54 (5.2), 47 (8.4), 44 (9.3), 43 (88.
7), 42 (53.8), 41 (100), 40 (7.0)

[0023]

As described in detail above, the present invention relates to a method for producing a perfluorocarboxylic acid ester, which comprises heating and reacting a perfluorocarboxylic acid and an olefin without a solvent. According to the olefin and perfluorocarboxylic acid as starting materials,
It is possible to synthesize the perfluorocarboxylic acid secondary alcohol ester almost quantitatively regioselectively. The resulting perfluorocarboxylic acid alcohol ester is also important as a detergent, a water repellent, a lubricant, or a liquid crystal material.

Continuing from the front page (72) Inventor Kunio Okuhara 2-40-17 Hongo, Bungo-ku, Tokyo Hongo Wakai Building 6F 6F, New Refrigerant Project, etc. JP-A-5-65248 (JP, A) JP-B-53-6131 (JP, B1) Bull. Chem. Soc. Japan, 65 [7] (1992), 1976-1981. (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 69/63 C07C 67/04 C07D 207/10 C07D 265/30 BEILSTEIN (STN ) CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (4)

(57) [Claims] 1. A method for producing a perfluorocarboxylic acid ester, wherein an addition reaction of a perfluorocarboxylic acid to an olefin is carried out by causing a perfluorocarboxylic acid and an olefin to undergo a heat reaction without a solvent. 2. A linear or branched perfluoroalkyl group-containing compound having 1 to 20 carbon atoms, which may be substituted with a substituent having a perfluorocyclic structure containing a hetero atom such as oxygen or nitrogen. Item 1. The method for producing a perfluorocarboxylic acid ester from a perfluorocarboxylic acid according to Item 1. 3. The method for producing a perfluorocarboxylic acid ester from an olefin according to claim 1, wherein the olefin is a linear or branched olefin having 1 to 20 carbon atoms which may be substituted with a functional group such as a carboxyl group. . 4. The method for producing a perfluorocarboxylic acid ester from an olefin according to claim 1, wherein the perfluorocarboxylic acid and the olefin are heated and reacted at a temperature of 120 to 160 ° C.