FLUORINE-CONTAINING ETHER MONOCARBOXYLIC ACID AMINOALKYL ESTER AND A METHOD FOR PRODUCING THE SAME

Abstract

A fluorine-containing ether monocarboxylic acid aminoalkyl ester represented by the general formula:

C.sub.nF.sub.2n+1O[CF(CF.sub.3)CF.sub.2O].sub.aCF(CF.sub.3)COO(CH.sub.2).sub.bNR.sup.1R.sup.2

(wherein R.sup.1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group, preferably an alkyl group having 1to 6 carbon atoms or an aryl group; R.sup.2 is an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group, preferably an alkyl group having 1to 6 carbon atoms or an aryl group; n is an integer of 1 to 3; a is an integer of 2 to 20, preferably an integer of 4 to 10; and b is an integer of 1 to 12, preferably an integer of 1 to 3). Such a fluorine-containing ether monocarboxylic acid ester having an amino group at the end of the ester group is produced by reacting a perfluoroether carboxylic acid fluoride compound C.sub.nF.sub.2n+1O[CF(CF.sub.3)CF.sub.2O].sub.1CF(CF.sub.3)COF and a hydroxyalkyl amine compound HO(CH.sub.2).sub.bNR.sup.1R.sup.2 in the presence of an alkali metal fluoride.

Claims

1. A fluorine-containing ether monocarboxylic acid aminoalkyl ester represented by the general formula:
C.sub.nF.sub.2n+1O[CF(CF.sub.3)CF.sub.2O].sub.aCF(CF.sub.3)COO(CH.sub.2).sub.bNR.sup.1R.sup.2 [I] wherein R.sup.1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group; R.sup.2 is an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group; n is an integer of 1 to 3; a is an integer of 2 to 20; and b is an integer of 1 to 12.

2. The fluorine-containing ether monocarboxylic acid aminoalkyl ester according to claim 1, wherein a is an integer of 4 to 10, and b is an integer of 1 to 3.

3. A method for producing the fluorine-containing ether monocarboxylic acid aminoalkyl ester according to claim 1, comprising reacting a perfluoroether carboxylic acid fluoride compound represented by the general formula:
C.sub.nF.sub.2n+1O[CF(CF.sub.3)CF.sub.2O].sub.aCF(CF.sub.3)COF [II] wherein n is an integer of 1 to 3, and a is an integer of 2 to 20; and a hydroxyalkyl amine compound represented by the general formula:
HO(CH.sub.2).sub.bNR.sup.1R.sup.2 [Ill] wherein R.sup.1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group; R.sup.2 is an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group; and b is an integer of 1 to 12; in the presence of an alkali metal fluoride.

4. The method for producing the fluorine-containing ether monocarboxylic acid aminoalkyl ester according to claim 3, wherein after completion of the reaction, the reaction mixture is treated with an alkali metal hydroxide aqueous solution.

Description

EXAMPLES

[0034] The following describes the present invention with reference to Examples.

Example 1

[0035] 200 g (191 mmol) of C.sub.3F.sub.7O[CF(CF.sub.3)CF.sub.2O].sub.4CF(CF.sub.3)COF (95.0 GC %), 900 ml of a fluorine-containing solvent (Novec HFE-7200, produced by Sumitomo 3M Ltd.), and 16.0 g (381 mmol) of sodium fluoride were charged in a 1L flask equipped with a stirring blade, a thermometer, a dropping funnel, and a reflux condenser in a nitrogen atmosphere. After the mixture was cooled to 50 C. or less in an ice bath, 17.9 g (201 mmol) of N,N-dimethylethanolamine (100 GC %) was slowly added dropwise from the dropping funnel, while maintaining the temperature at 10 C. or less.

[0036] After completion of the dropwise addition, the sodium fluoride was removed by a pressure filtering device, and the reaction mixture was then returned to the above reactor and cooled to 0 C. Then, 1000 g of a 2 wt. % NaOH aqueous solution, which had previously been cooled to 5 C., was slowly added thereto. After stirring the mixture for 15 minutes, the organic phase was collected and washed with 1000 g of 5 C. water. The fluorine-containing solvent in the organic phase was distilled off under reduced pressure by an evaporator, and a yellow, highly viscous residue was obtained. The highly viscous residue was subjected to simple distillation, thereby obtaining 189 g (yield: 93.2%) of the following fluorine-containing ether monocarboxylic acid aminoalkyl ester compound of a pale yellow, highly viscous liquid state.

CF.sub.3CF.sub.2CF.sub.2O [CF(CF.sub.3)CF.sub.2O] .sub.4CF(CF.sub.3)COO(CH.sub.2).sub.2N(CH.sub.3).sub.2

[0037] .sup.19FNMR (acetone-d6, CFCl.sub.3 standard, ppm):

TABLE-US-00001 = 80.0~85.6 CF.sub.2O (m, 10F) 82.4 CF(CF.sub.3)COO (s, 3F) 83.0 CF(CF.sub.3)CF.sub.2O (s, 3F) 83.2 CF.sub.3CF.sub.2 (s, 3F) 131.4 CF.sub.3CF.sub.2CF.sub.2O (s, 2F) 133.1 CF(CF.sub.3)COO (t, 1F) 145.0~145.9 CF(CF.sub.3)CF.sub.2O (m, 4F)

[0038] .sup.1HNMR (acetone-d6, TMS standard, ppm):

TABLE-US-00002 = 4.30 OCH.sub.2 (t, 2H) 2.44 CH.sub.2N (m, 2H) 2.28 CH.sub.3 (s, 6H) IR: 1792 cm.sup.1 CO vibration

Example 2

[0039] In Example 1, the reaction and purification were carried out using 200 g (105 mmol) of a compound represented by the following formula:

[0040] C.sub.3F.sub.7O[CF(CF.sub.3)CF.sub.2O].sub.aCF(CF.sub.3)COF a: 9.5 (NMR number average) as the perfluoroether carboxylic acid fluoride compound, and 17.9 g (175 mmol) of N-dimethylaminopropanol (100 GC %) as the hydroxyalkyl amine compound, thereby obtaining 153 g (yield: 73%) of the following fluorine-containing ether monocarboxylic acid aminoalkyl ester compound of a pale yellow, highly viscous liquid state.

CF.sub.3CF.sub.2CF.sub.2O[CF(CF.sub.3)CF.sub.2O].sub.aCF(CF.sub.3)COO(CH.sub.2).sub.3N(CH.sub.3).sub.2

[0041] a:9.5 (NMR number average)

[0042] .sup.19FNMR (acetone-d6, CFCl.sub.3 standard, ppm):

TABLE-US-00003 = 80.0, 85.6 CF.sub.2O (m) 82.3 CF(CF.sub.3)COO (s, 3F) 83.1 CF(CF.sub.3)CF.sub.2O (s) 83.3 CF.sub.3CF.sub.2 (s, 3F) 131.4 CF.sub.3CF.sub.2CF.sub.2O (s, 2F) 133.1 CF(CF.sub.3)COO (t, 1F) 145.0~145.9 CF(CF.sub.3)CF.sub.2O (m, 7.5F)

[0043] .sup.1HNMR (acetone-d6, TMS standard, ppm):

TABLE-US-00004 = 4.28 OCH.sub.2 (t, 2H) 2.78 CH.sub.2N (m, 2H) 2.28 CH.sub.3 (s, 6H) 1.77 CH.sub.2CH.sub.2CH.sub.2N (m, 2H) IR: 1790 cm.sup.1 CO vibration