Separation method

Abstract

To provide a method capable of separating a monofunctional species, bifunctional species, etc. of a fluorinated ether compound having a polyfluoropolyether chain and a predetermined functional group in good yield and with high separation performance. A separation method for separating a compound represented by the formula (1) and a compound represented by the formula (2) from a mixture containing them by chromatography using a stationary phase and a mobile phase, wherein the mobile phase contains at least one type of specific solvent selected from a hydrofluoroolefin, a hydrochlorofluoroolefin, a chlorofluoroolefin, a cyclic hydrofluoroolefin, a cyclic hydrochlorofluoroolefin, a cyclic chlorofluoroolefin, a cyclic hydrofluorocarbon, a cyclic hydrochlorofluorocarbon, a cyclic chlorofluorocarbon and a perfluoroketone:
A-(OX).sub.mOZ(R).sub.n1Formula (1)
(R).sub.n2Z(OX).sub.mOZ(R).sub.n3Formula (2)

Claims

1. A separation method for separating a compound represented by the following formula (1) and a compound represented by the following formula (2) from a mixture containing them by chromatography using a mobile phase and a stationary phase, which comprises a step of supplying the mixture to the stationary phase of the chromatography to let it be adsorbed on the stationary phase, and a step of supplying, to the stationary phase having the mixture adsorbed thereon, a mobile phase containing at least one type of specific solvent selected from the group consisting of a hydrofluoroolefin, a hydrochlorofluoroolefin, a chlorofluoroolefin, a cyclic hydrofluoroolefin, a cyclic hydrochlorofluoroolefin, a cyclic chlorofluoroolefin, a cyclic hydrofluorocarbon, a cyclic chlorofluorocarbon and a perfluoroketone:
A-(OX).sub.mOZ(R).sub.n1Formula (1)
(R).sub.n2Z(OX).sub.mOZ(R).sub.n3Formula (2) where A is an alkyl group or a fluoroalkyl group, X is an alkylene group or a fluoroalkylene group having one or more fluorine atoms, m is an integer of 2 or more, Z is a (n1+1)-valent, (n2+1)-valent or (n3+1)-valent linking group, R is any functional group selected from the group consisting of OH, CR.sup.1CR.sup.2R.sup.3 (where R.sup.1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and R.sup.2 and R.sup.3 are each independently a hydrogen atom or a fluorine atom), CH.sub.3, NH.sub.2, SH, -Ph, F, Cl, Br, I, CCH and N.sub.3, n1 is an integer of 1 or more, n2 is an integer of 1 or more, and n3 is an integer of 1 or more.

2. The separation method according to claim 1, wherein in the above formulas (1) and (2), A is a fluoroalkyl group, and X is a fluoroalkylene group having one or more fluorine atoms.

3. The separation method according to claim 1, wherein in the above formulas (1) and (2), n1, n2 and n3 are the same integers.

4. The separation method according to claim 1, wherein the mixture further contains a compound represented by the following formula (3), and it is separated into the compound represented by the formula (1), the compound represented by the formula (2), and the compound represented by the formula (3):
A-(OX).sub.mO-AFormula (3) where A, X, and m are the same as those in the above formulas (1) and (2).

5. The separation method according to claim 1, wherein the specific solvent is a solvent that does not contain chlorine atoms.

6. The separation method according to claim 1, wherein the specific solvent includes at least one type selected from the group consisting of a hydrofluoroolefin, a cyclic hydrofluoroolefin and a cyclic hydrofluorocarbon.

7. The separation method according to claim 1, wherein in the above formulas (1), (2) and (3), (OX).sub.m contains the following structure: {(OCF.sub.2).sub.m21.Math.(OCF.sub.2CF.sub.2).sub.m22} where m21 is an integer of 1 or more, m22 is an integer of 1 or more, and m21+m22 is an integer of from 2 to 500.

8. The separation method according to claim 1, wherein the stationary phase is selected from the group consisting of aluminum oxide, silica gel, magnesium oxide, aluminum silicate, magnesium silicate, chemically modified silica gel and diatomaceous earth.

9. The separation method according to claim 1, wherein the chromatography is column chromatography.

Description

EXAMPLES

(1) In the following, the present invention will be described in detail with reference to Examples. Ex. 1 to Ex. 32 are Examples of the present invention, and Ex. 33 to Ex. 37 are Comparative Examples. However, the present invention is not limited to these Examples. The content (%) of each component in Table 1 given below indicates the mass standard.

(2) Further, the structures of the fluorinated compounds used in Examples are as shown below.

(3) (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.x type

(4) 0-functional species: CF.sub.3O(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.xl-CF.sub.3 Monofunctional species: CF.sub.3O(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.x2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2X Bifunctional species: XCF.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.x3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2X X is the terminal functional group, the mass average molecular weight of the structure other than X is 4,800, and the repeating units: x1, x2=14.5.
(CF.sub.2O).sub.n.Math.(CF.sub.2CF.sub.2O).sub.m type 0-functional species: CF.sub.3O(CF.sub.2O).sub.n.Math.(CF.sub.2CF.sub.2O).sub.mCF.sub.3 Monofunctional species: CF.sub.3O(CF.sub.2O).sub.n.Math.(CF.sub.2CF.sub.2O).sub.mX Bifunctional species: X(CF.sub.2O).sub.n.Math.(CF.sub.2CF.sub.2O).sub.mX X is the terminal functional group, and the mass average molecular weight of the structure other than X is 4,500, and the repeating units: n=25, and m=22.

Synthesis of Fluorinated Compounds

Synthesis Example 1

(5) Synthesis Example 1-1

(6) The following compound (A-1) was obtained by the method described in Example 7 of WO2013/121984. CF.sub.3O(CF.sub.2CFHOCF.sub.2CF.sub.2CF.sub.2CH.sub.2O).sub.a1-H: A-1 Repeating unit a1=14.5
Synthesis Example 1-2

(7) In a 200-mL three-necked flask, 30 g of compound (A-1), 1 g of a 48% KOH solution, 1.1 g of water and 0.55 g of tert-butyl alcohol were mixed at 80 C. for 10 minutes. To the obtained mixed liquid, 2.4 g of perfluoropropyl vinyl ether was dropwise added and mixed at 80 C. for 4 hours. After cooling the mixed liquid to room temperature, 60 g of AC-2000 (C.sub.6F.sub.13H: manufactured by AGC Inc.) was added, and further, in an ice bath, 6.5 g of 2N hydrochloric acid was dropwise added. The mixed liquid was transferred to a 200-mL separating funnel and allowed to stand for 1 hour. The lower phase was withdrawn and put into a new 200-mL separating funnel, and 87 g of water was added, followed by stirring. After being left to stand for 1 hour, the lower phase was recovered and concentrated to obtain the following compound (A-2). CF.sub.3O(CF.sub.2CFHOCF.sub.2CF.sub.2CF.sub.2CH.sub.2O).sub.a2-CF.sub.2CF.sub.2CF.sub.3: A-2 Repeating unit a2=14.5
Synthesis Example 1-3

(8) An autoclave (made of nickel, internal volume 500 mL) was prepared, and at the gas outlet of the autoclave, a cooler maintained at 0 C., a NaF pellet filled layer and a cooler maintained at 10 C. were installed in series. Further, a liquid returning line to return a liquid flocculated from the cooler maintained at 10 C. back to the autoclave was installed.

(9) In the above autoclave, 312 g of R-113 (CF.sub.2ClCFCl.sub.2) was put, followed by stirring while maintaining the temperature at 25 C. After blowing nitrogen gas into the autoclave at 25 C. for 1 hour, 20% fluorine gas was blown into the autoclave at 25 C. at a flow rate of 2.0 L/hour for 1 hour. Next, while blowing 20% fluorine gas at the same flow rate, a solution having 8.4 g of compound (A-2) dissolved in 84 g of R-113, was injected to the autoclave over 3.6 hours.

(10) Then, while blowing 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was pressurized to 0.15 MPa (gauge pressure). Into the autoclave, 9 mL of a benzene solution containing 0.015 g/mL of benzene in R-113 was injected while heating from 25 C. to 40 C., and the benzene solution inlet of the autoclave was closed. After stirring for 15 minutes, 6 mL of the benzene solution was injected again while maintaining the temperature at 40 C., and the inlet was closed. The same operation was repeated three more times. The total amount of benzene injected was 0.33 g.

(11) Further, while 20% fluorine gas was blown into the autoclave at the same flow rate, stirring was continued for 1 hour. Then, the pressure in the autoclave was brought to atmospheric pressure, and nitrogen gas was blown into the autoclave for 1 hour. The content of the autoclave was concentrated by an evaporator to obtain 8.8 g of the following compound (A-3) of 0-functional species. CF.sub.3O(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.a3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O-CF.sub.2CF.sub.2CF.sub.3: A-3 Repeating unit a3=14.5
Synthesis Example 1-4

(12) The following compound (B-1) of monofunctional species was obtained by the method described in Example 7 of WO2013/121984. CF.sub.3O(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.b1CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CH.sub.2OH: (B-1) Repeating unit b1=14.5
Synthesis Example 1-5

(13) In a 200-mL egg plant flask, 16.2 g of HOCH.sub.2CF.sub.2CF.sub.2CH.sub.2OH and 13.8 g of potassium carbonate were put, followed by stirring at 120 C., and 278 g of the compound (A-1) obtained in Synthesis Example 1-1 was added, followed by stirring at 120 C. for 2 hours. The temperature in the egg plat flask was set to 25 C., and 50 g each of AC-2000 and hydrochloric acid were added, followed by liquid separation, and the organic phase was concentrated. The obtained reaction crude liquid was purified by silica gel column chromatography to obtain 117.7 g of the following compound (C-1).

(14) ##STR00009## Repeating unit x1+x2=13.5
Synthesis Example 1-6

(15) In a 50-mL egg plant flask, 20 g of compound (C-1), 7.1 g of a powder of sodium fluoride, 20 g of AC-2000 and 20 g of CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)COF were added. Then, under a nitrogen atmosphere, the mixed liquid was stirred at 50 C. for 24 hours. After the temperature in the egg plant flask was brought to 25 C., the sodium fluoride powder was removed by filtration. Excess CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)COF and AC-2000 were distilled off under reduced pressure to obtain 24 g of the following compound (C-2).

(16) ##STR00010## Repeating unit x1+x2=13.5
Synthesis Example 1-7

(17) In a 500-mL metal reactor, 250 mL of ClCF.sub.2CFClCF.sub.2OCF.sub.2CF.sub.2Cl (hereinafter referred to as CFE-419) was put and bubbled with nitrogen gas, then 20 vol % fluorine gas diluted with nitrogen gas was bubbled. A CFE-419 solution of the above compound (C-2) (concentration: 10%, compound (C-2): 24 g) was introduced over a period of 6 hours. The ratio of the introduction rate of fluorine gas (mol/hour) to the introduction rate of hydrogen atoms in compound (C-2) (mol/hour) was controlled to become 2:1. After the introduction of the compound (C-2) was finished, a CFE-419 solution of benzene (concentration: 0.1%, benzene: 0.1 g) was introduced intermittently. After the introduction of benzene was finished, fluorine gas was bubbled, and finally the inside of the reactor was fully replaced with nitrogen gas. The solvent was distilled off to obtain 25.3 g of the following compound (C-3).

(18) ##STR00011## Repeating unit x=14.5
Synthesis Example 1-8

(19) In a 50-mL egg plant flask, 25.3 g of compound (C-3), 2.2 g of sodium fluoride and 25 mL of AC-2000 were put, and in an ice bath, the mixed liquid was stirred. To the obtained mixed liquid, 1.7 g of methanol was put, followed by stirring at 25 C. for 1 hour. The mixed liquid was filtered, and the filtrate was purified by silica gel column chromatography. 15 g of the following compound (C-4) was obtained.

(20) ##STR00012## Repeating unit x=14.5
Synthesis Example 1-9

(21) In a 50-mL two-necked egg plant flask, 0.04 g of lithium aluminum hydride was suspended in 1.6 g of THF (tetrahydrofuran). While the mixed liquid was cooled in an ice bath, a solution having 6.1 g of the above compound (C-4) diluted by 6.0 g of AC 6000 (C.sub.6F.sub.13C.sub.2H.sub.5: manufactured by AGC Inc.), was slowly dropwise added. Thereafter, the ice bath was removed, and stirring was continued while the temperature was slowly raised to room temperature. After stirring at room temperature for 12 hours, an aqueous hydrochloric acid solution was dropwise added until the liquid became acidic. 15 mL of AK-225 was added, followed by washing once with water and once with saturated brine, to recover the organic phase. The recovered organic phase was concentrated by an evaporator to obtain 5.9 g of the following compound (C-5) of bifunctional species. HOCH.sub.2CF.sub.2CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.c5CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CH.sub.2 OH: C-5 Repeating unit x=14.5
Synthesis Example 1-10

(22) 5 g of compound (A-3) of 0-functional species, 86 g of compound (B-1) of monofunctional species, and 9 g of compound (C-5) of bifunctional species were mixed to make the sample mixtures for Ex. 1 to 16 and 35 to 37.

Synthesis Example 2

(23) Synthesis Example 2-1

(24) Fomblin M (product name of Solvay Solexis, Inc.) was purified by silica gel column chromatography to obtain the following compound (D-1) of 0-functional species. CF.sub.3O(CF.sub.2O).sub.n.Math.(CF.sub.2CF.sub.2O).sub.mCF.sub.3: D-1 Repeating unit n=25, m=22
Synthesis Example 2-2

(25) The following compound (E-1) was obtained in accordance with the method described in Ex. 1 of Examples (specifically Ex. 1-1 to Ex. 1-4) of WO2017/038830. CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2[(OCF.sub.2).sub.n.Math.(OCF.sub.2CF.sub.2).sub.m]OCF.sub.2C(O)OCH.sub.3: E-1 Repeating unit n=25, m=21

(26) Next, into a 300 cc three-necked round bottom flask, 2.4 g of sodium borohydride powder was put, and 15 g of AC-2000 (product name of AGC Inc.) was added. While cooling in an ice bath, the mixture was stirred, and under a nitrogen atmosphere, a solution having 30 g of the above compound (E-1), 4 g of methanol and 60 g of AC-2000 mixed, was slowly dropwise added from a dropping funnel so that the internal temperature did not exceed 10 C. After the total volume was dropped, another 4 g of methanol was dropwise added. Thereafter, the mixture was stirred at 10 C. for 1 hour. It was cooled again in an ice bath, and an aqueous hydrochloric acid solution was dropwise added until the liquid became acidic. After the reaction was completed, it was washed once with hydrochloric acid solution and once with water, and the organic phase was recovered.

(27) The recovered organic phase was concentrated by an evaporator. The recovered concentrated liquid was distilled off under reduced pressure and column purification was carried out to obtain 24 g of the following compound (E-2). CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2[(OCF.sub.2).sub.n.Math.(OCF.sub.2CF.sub.2).sub.m]OCF.sub.2CH.sub.2OH: E-2 Repeating unit n=25, m=21
Synthesis Example 2-3

(28) The following compound (F-1) of bifunctional species was obtained by purifying Fomblin D4000 (product name of Solvay Solexis, Inc.) by silica gel column chromatography. HOCH.sub.2(CF.sub.2O){(CF.sub.2O).sub.n.Math.(CF.sub.2CF.sub.2O).sub.m}CF.sub.2CH.sub.2OH: F-1 Repeating unit n=25, m=22
Synthesis Example 2-4

(29) 15 g of compound (D-1) of 0-functional species, 55 g of compound (E-2) of monofunctional species and 30 g of compound (F-1) of bifunctional species were mixed to make the mixtures of Ex. 17 to Ex. 25.

(30) Synthesis Example 2-5

(31) 5 g of compound (D-1) of 0-functional species, 86 g of compound (E-2) of monofunctional species and 9 g of compound (F-1) of bifunctional species were mixed to make the mixture in Ex. 32.

Synthesis Example 3

(32) Synthesis Example 3-1

(33) The following compound (G-1) was obtained by the method described in Example 6 of WO2013/121984. CF.sub.3O(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.g1CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2C(O)OCH.sub.3: G-1 Repeating unit g1=14.5
Synthesis Example 3-2

(34) In a 300-mL four-necked flask equipped with a Dimroth condenser, a dropping funnel, a thermometer and a magnetic stirrer, 40 g of compound (G-1), 25 g of a diethyl ether solution of allylmagnesium bromide (bromo group concentration: 0.05 mol/100 g), 40 g of 1,3-bisfluoromethylbenzene and 13 g of tetrahydrofuran were charged, and the inside of the flask was replaced with nitrogen. While stirring, the obtained mixed liquid was reacted at an internal temperature of 60 C. for 6 hours and cooled to room temperature (20 C.). After that, the mixed liquid was added to a separating funnel covered with hydrochloric acid water (hydrochloric acid water having 6 g of 12N hydrochloric acid and 54 g of water mixed), followed by stirring for 30 minutes, and then the lower layer was recovered. The recovered liquid was subjected to evaporation under a condition of 110 C./1 mmHg to remove the solvent component, followed by purification by silica gel column chromatography to obtain 35 g of the following compound (G-2) of monofunctional species. CF.sub.3O(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.g2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2C(OH)(CH.sub.2CHCH.sub.2).sub.2: G-2 Repeating unit g2=14.5
Synthesis Example 3-3

(35) In a 300-mL four-necked flask equipped with a Dimroth condenser, a dropping funnel, a thermometer and a magnetic stirrer, 40 g of compound (C-4), 50 g of a diethyl ether solution of allylmagnesium bromide (bromo group concentration: 0.05 mol/100 g), 40 g of 1,3-bisfluoromethylbenzene and 13 g of tetrahydrofuran, were charged, and the inside of the flask was replaced with nitrogen. While stirring, the obtained mixed liquid was reacted at an internal temperature of 60 C. for 6 hours and cooled to room temperature (20 C.). After that, the mixed liquid was added slowly to a separating funnel filled with hydrochloric acid water (hydrochloric acid water having 6 g of 12N hydrochloric acid and 54 g of water mixed), stirred for 30 minutes, and the lower layer was recovered. The recovered liquid was subjected to evaporation under a condition of 110 C./1 mmHg to remove the solvent component, followed by purification by silica gel column chromatography to obtain 35 g of the following compound (H-1) of bifunctional species.

(36) ##STR00013## Repeating unit x=14.5
Synthesis Example 3-4

(37) 5 g of the above compound (A-3) of 0-functional species, 86 g of the above compound (G-2) of monofunctional species and 9 g of the above compound (H-1) of bifunctional species were mixed to make the sample mixed liquid of Ex. 26.

Synthesis Example 4

(38) Synthesis Example 4-1

(39) 5 g of the above compound (A-3) of 0-functional species, 86 g of the above compound (G-1) of monofunctional species and 9 g of the above compound (C-4) of bifunctional species were mixed to make the sample mixture of Ex. 27.

Synthesis Example 5

(40) Synthesis Example 5-1

(41) In a 200 cc egg plant flask, 0.67 g of HO(CO)C(CH.sub.2CHCH.sub.2).sub.3, 33 mL of dichloromethane and 0.67 mL of oxalyl chloride were added, followed by stirring under cooling with ice, and then, 0.0393 g of DMF (N,N-dimethylformamide) was added. Then, the mixed liquid was stirred at room temperature and concentrated to obtain 0.6 g of Cl(CO)C(CH.sub.2CHCH.sub.2).sub.3.

(42) Separately, in a 50 cc egg plant flask, 7 g of compound B-1, 7 g of AC-6000, 0.4 g of triethylamine and 0.2 g of N,N-dimethyl-4-aminopyrdine were added, and further, 0.6 g of the above Cl(CO)C(CH.sub.2CHCH.sub.2).sub.3 was added, and the mixed liquid was stirred at 30 C. The obtained mixed liquid was purified by silica gel column chromatography to obtain 5.8 g of the following compound (1-1) of monofunctional species. CF.sub.3O(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.i1CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CH.sub.2O(CO)C(CH.sub.2CHC H2).sub.3: I-1 Repeating unit i1=14.5
Synthesis Example 5-2

(43) In a 200 cc egg plant flask, 0.67 g of HO(CO)C(CH.sub.2CHCH.sub.2).sub.3, 33 mL of dichloromethane and 0.67 mL of oxalyl chloride were added, followed by stirring under cooling with ice, and then, 0.0393 g of DMF (N,N-dimethylformamide) was added. Then, the mixed liquid was stirred at room temperature and concentrated to obtain 0.6 g of Cl(CO)C(CH.sub.2CHCH.sub.2).sub.3.

(44) Synthesis Example 5-3

(45) Separately, in a 50 cc egg plant flask, 3.5 g of compound C-5, 7 g of AC-6000, 0.4 g of triethylamine and 0.2 g of N,N-dimethyl-4-aminopyddine were added, and 0.6 g of the above Cl(CO)C(CH.sub.2CHCH.sub.2).sub.3 was added, and the mixed liquid was stirred at 30 C. The obtained mixed liquid was purified by silica gel column chromatography to obtain 2.4 g of the following compound (J-1) of bifunctional species.

(46) ##STR00014## Repeating unit x=14.5
Synthesis Example 5-4

(47) 5 g of compound (A-3) of 0-functional species, 86 g of compound (1-1) of monofunctional species and 9 g of compound (J-1) of bifunctional species were mixed to make the sample mixture of Ex. 28.

Synthesis Example 6

(48) Synthesis Example 6-1

(49) The following compound (K-1) of monofunctional species was obtained by the method described in Example 11 of WO2017/038830. CF.sub.3O(CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O).sub.k1(CF.sub.2CF.sub.2O)CF.sub.2CF.sub.2CF.sub.2C(O)NHCH.sub.2C(CH.sub.2 CHCH.sub.2).sub.3: K-1 Repeating unit k1=14.5
Synthesis Example 6-2

(50) In a 50-mL egg plant flask, 15 g of compound (C-4), 3.2 g of H.sub.2NCH.sub.2C(CH.sub.2CHCH.sub.2).sub.3 and 15 mL of AC-2000 were put, and the mixed liquid was stirred at 0 C. for 24 hours. The mixed liquid was purified by silica gel column chromatography. 11.2 g of the following compound (L-1) of bifunctional species was obtained.

(51) ##STR00015## Repeating unit x=14.5
Synthesis Example 6-3

(52) 5 g of compound (A-3) of 0-functional species, 86 g of compound (K-1) of monofunctional species and 9 g of compound (L-1) of bifunctional species were mixed to make the sample mixture of Ex. 29.

Synthesis Example 7

(53) Synthesis Example 7-1

(54) In a 100 cc pressure-resistant reactor, 15 g of compound G-1, 50 g of ASAHIKLIN AK-225 (product name of AGC Inc.) and 7.5 g of a 2.0 M ammonia-methanol solution were put, and the mixed liquid was stirred at room temperature for 6 hours. Thereafter, the solvent was removed from the mixed liquid to obtain 14.8 g of the desired compound (M-1) of monofunctional species. CF.sub.3(OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.m1OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2C(O)NH.sub.2: M-1 Repeating unit m1=14.5
Synthesis Example 7-2

(55) In a 100 cc pressure-resistant reactor, 15 g of compound C-4, 50 g of ASAHIKLIN AK-225 (product name of AGC Inc.) and 15 g of a 2.0 M ammonia-methanol solution were put, and the mixed liquid was stirred at room temperature for 6 hours. Thereafter, the solvent was removed from the mixed liquid to obtain 14.8 g of the desired compound (N-1) of bifunctional species.

(56) ##STR00016## Repeating unit x=14.5
Synthesis Example 7-3

(57) 5 g of the above compound (A-3) of 0-functional species, 86 g of the above compound (M-1) of monofunctional species and 9 g of the above compound (N-1) of bifunctional species were mixed to make the sample mixture of Ex. 30.

Synthesis Example 8

(58) Synthesis Example 8-1

(59) In a 300 cc egg plant flask, 1.5 g of compound M-1, 75 g of AK-225 and 30 g of diethyl ether were added, followed by stirring under an ice bath. Thereafter, 0.31 g of lithium aluminum hydride was slowly added to the obtained mixed liquid, followed by stirring at room temperature for 20 hours. Thereafter, 0.3 cc of a saturated aqueous sodium sulfate solution was added to the mixed liquid, and the precipitated solid was removed by celite filtration. The obtained filtrate was concentrated and then purified by silica gel column chromatography to obtain 6.8 g of the desired compound (O-1). CF.sub.3(OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.o1OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CH.sub.2NH.sub.2: O-1 Repeating unit o1=14.5
Synthesis Example 8-2

(60) Separately, in a 50 cc egg plant flask, 3.0 g of compound (A-3) and 0.35 mL of triethylamine were added, and 0.45 g of Cl(CO)C(CH.sub.2CHCH.sub.2).sub.3 synthesized in Synthesis Example 5-1 and 2 mL of 1,3-bisfluoromethylbenzene were added. The mixed liquid was stirred for 1 hour, and the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain 1.7 g of the desired compound (O-2) of monofunctional species. CF.sub.3(OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.o20CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CH.sub.2NH(CO)C(CH.sub.2CHCH.sub.2).sub.3: O-2 Repeating unit o2=14.5
Synthesis Example 8-3

(61) In a 300 cc egg plant flask, 15 g of compound (N-1), 75 g of AK-225 and 30 g of diethyl ether were added, followed by stirring under an ice bath. Thereafter, 0.62 g of lithium aluminum hydride was slowly added to the mixed liquid, followed by stirring at room temperature for 20 hours. Thereafter, 0.6 cc of a saturated aqueous sodium sulfate solution was added to the mixed liquid, and the precipitated solid was removed by celite filtration. The obtained filtrate was concentrated and then purified by silica gel column chromatography to obtain 6.8 g of the desired compound (P-1).

(62) ##STR00017## Repeating unit x=14.5
Synthesis Example 8-4

(63) Separately, in a 50 cc egg plant flask, 3.0 g of compound (P-1) and 0.7 mL of triethylamine were added, and 0.45 g of Cl(CO)C(CH.sub.2CHCH.sub.2).sub.3 synthesized in Synthesis Example 5-3 and 2 mL of 1,3-bistrifluoromethylbenzene were added. The mixture was stirred for 1 hour, and the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain 1.7 g of the following compound (P-2) of bifunctional species.

(64) ##STR00018## Repeating unit x=14.5
Synthesis Example 8-5

(65) 5 g of compound (A-3) of 0-functional species, 86 g of compound (O-2) of monofunctional species and 9 g of compound (P-2) of bifunctional species were mixed to make the sample mixture of Ex. 31.

(66) Synthesis Example 9-1

(67) In a 300-mL egg plant flask, 100 g of compound (F-1), 14.9 g of cesium carbonate and 100 g of 1 3-bis(trifluoromethyl)benzene were put, and 6.4 g of propyl p-toluenesulfonate was added. The mixture was stirred at 80 C. for 8 hours under a nitrogen atmosphere. It was washed with dilute hydrochloric acid solution, and the organic layer was recovered and concentrated by an evaporator to obtain a crude product, which was purified by silica gel chromatography, to obtain a mixture containing 15.2 g, 55.3 g and 29.5 g, respectively, of the following compound (Q-1) of 0-functional species, compound (Q-2) of monofunctional species and compound (F-1) of bifunctional species. CH.sub.3CH.sub.2CH.sub.2OCH.sub.2(CF.sub.2O){(CF.sub.2O).sub.n(CF.sub.2CF.sub.2O).sub.m}CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.3: (Q-1) HOCH.sub.2(CF.sub.2O){(CF.sub.2O).sub.n(CF.sub.2CF.sub.2O).sub.m}CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.3: (Q-2) HOCH.sub.2(CF.sub.2O){(CF.sub.2O).sub.n.Math.(CF.sub.2CF.sub.2O).sub.m}CF.sub.2CH.sub.2OH: (F-1)
(Separation Method)

(68) Sample mixtures of Ex. 1 to 37 prepared as described above were separated by a column chromatography method.

(69) In a column of 2 cm in diameter and 70 cm in height, a mixture of the solvent (200 g) to be used as the mobile phase and silica gel (50 g) was put, and then, 200 g of a solvent to be used as a mobile phase was permitted to flow to prepare a stationary phase.

(70) Thereafter, a mixture of the sample mixture (10 g) from one of the above Ex. 1 to 37 and the solvent (5 g) to be used as the mobile phase was adsorbed onto the stationary phase at the top of the column. Then, from the top of the column, the solvent as the mobile phase was pushed down at N.sub.2 pressure (gauge pressure) of 0.1 MPa, and 1,000 g of the solution was recovered as the first fraction. This recovered material was concentrated and analyzed by using high performance liquid chromatography (HPLC, manufactured by Shimadzu Corporation). Further, a solvent having the solvent used earlier as the mobile phase and acetone mixed in the mass ratio of 1:1, was pushed down, and 500 g of the solution was recovered as the second fraction. This was concentrated and analyzed by using HPLC.

(71) The specific solvents used as the above mobile phase are as shown below. Solvent 1: CF.sub.3CFCCl.sub.2 (CFO) Solvent 2: CFCl.sub.2CFCF.sub.2 (CFO) Solvent 3: CF.sub.2HCFCHCl(HCFO) Solvent 4: CF.sub.3CHCHCl(Z) (HCFO) Solvent 5: CF.sub.3CHCHCl(E) (HCFO) Solvent 6: CClF.sub.2CFCHCl(HCFO) Solvent 7: CHF.sub.2CF.sub.2CF.sub.2CFCHCl(HCFO) Solvent 8: CF.sub.3CH.sub.2CFCH.sub.2 (HFO) Solvent 9: CF.sub.3CHCHCF.sub.3(E) (HFO) Solvent 10: CF.sub.3CHCHCF.sub.3(Z) (HFO) Solvent 11: Compound of the following formula (cyclic HFC)

(72) ##STR00019## Solvent 12: Compound of the following formula (cyclic CFO)

(73) ##STR00020## Solvent 13: Compound of the following formula (cyclic CFO)

(74) ##STR00021## Solvent 14: CF.sub.3CF.sub.2COCF(CF.sub.3).sub.2 (PFK) Solvent 15: (CF.sub.3).sub.2CFCOCF(CF.sub.3).sub.2 (PFK) Solvent 16: CF.sub.3CF.sub.2CF.sub.2OCFCF.sub.3COCF(CF.sub.3).sub.2 (PFK) Solvent 17: Mixed liquid of 95 wt % of CF.sub.3CFCCl.sub.2 (CFO) and 5 wt % of hexane (hydrocarbon (HC)) Solvent 18: C.sub.6F.sub.14 (perfluorocarbon (PFC)) Solvent 19: Hexane (hydrocarbon (HC)) Solvent 20: ASAHIKLIN AK-225 (product name of AGC Inc., hydrochlorofluorocarbon (HCFC))

(75) The main points in the separation with respect to the sample mixtures of the above Ex. 1 to 37 and the results obtained respectively are shown in the following Tables 1 to 3. Further, the yield in Table 3 represents the recovery rate (mass %) of each fraction relative to the charged mass (each component before separation).

(76) TABLE-US-00001 TABLE 1 Ex. A- O-Z-(R)n Repeating structure of main chain 1 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 2 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 3 Fluoroalkyl group O(CF.sub.3).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 4 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 5 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 6 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 7 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 8 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 9 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 10 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 11 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 12 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 13 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 14 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 15 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 16 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 17 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 18 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 19 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 20 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 21 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 22 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 23 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 24 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 25 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n (CF.sub.2CF.sub.2O)m 26 Fluoroalkyl group O(CF.sub.2).sub.3O(OH)(CH.sub.2CHCH.sub.2).sub.2 (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 27 Fluoroalkyl group O(CF.sub.2).sub.3COOCH.sub.3 (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 28 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OC(O)C(CH.sub.2CHCH.sub.2).sub.2 (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 29 Fluoroalkyl group O(CF.sub.2).sub.3CONHCH.sub.2C(CH.sub.2CHCH.sub.2).sub.3 (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 30 Fluoroalkyl group O(CF.sub.2).sub.3CONH.sub.2 (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 31 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2NHCOC(CH.sub.2CHCH.sub.2).sub.3 (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 32 Fluoroalkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 33 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 34 Alkyl group O(CF.sub.2)CH.sub.2OH (CF.sub.2O)n(CF.sub.2CF.sub.2O)m 35 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 36 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x 37 Fluoroalkyl group O(CF.sub.2).sub.3CH.sub.2OH (CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2O)x

(77) TABLE-US-00002 TABLE 2 Before separation Concentration (wt %) of 0-, mono- and bi-functional species 0-functional monofunctional bifunctional Mobile Ex. species species species phase Type 1 5.0 86.0 9.0 Solvent 1 CFO 2 5.0 86.0 9.0 Solvent 2 CFO 3 5.0 86.0 9.0 Solvent 3 HCFO 4 5.0 86.0 9.0 Solvent 4 HCFO 5 5.0 86.0 9.0 Solvent 5 HCFO 6 5.0 86.0 9.0 Solvent 6 HCFO 7 5.0 86.0 9.0 Solvent 7 HCFO 8 5.0 86.0 9.0 Solvent 8 HFO 9 5.0 86.0 9.0 Solvent 9 HFO 10 5.0 86.0 9.0 Solvent 10 HFO 11 5.0 86.0 9.0 Solvent 11 Cyclic HFC 12 5.0 86.0 9.0 Solvent 12 Cyclic CFO 13 5.0 86.0 9.0 Solvent 13 Cyclic CFO 14 5.0 86.0 9.0 Solvent 14 PFK 15 5.0 86.0 9.0 Solvent 15 PFK 16 5.0 86.0 9.0 Solvent 16 PFK 17 15.0 55.0 30.0 Solvent 1 CFO 18 15.0 55.0 30.0 Solvent 2 CFO 19 15.0 55.0 30.0 Solvent 3 HCFO 20 15.0 55.0 30.0 Solvent 4 HCFO 21 15.0 55.0 30.0 Solvent 5 HCFO 22 15.0 55.0 30.0 Solvent 6 HCFO 23 15.0 55.0 30.0 Solvent 7 HCFO 24 15.0 55.0 30.0 Solvent 8 HFO 25 15.0 55.0 30.0 Solvent 11 Cyclic HFC 26 5.0 86.0 9.0 Solvent 1 CFO 27 5.0 86.0 9.0 Solvent 1 CFO 28 5.0 86.0 9.0 Solvent 1 CFO 29 5.0 86.0 9.0 Solvent 1 CFO 30 5.0 86.0 9.0 Solvent 1 CFO 31 5.0 86.0 9.0 Solvent 1 CFO 32 5.0 86.0 9.0 Solvent 1 CFO 33 5.0 86.0 9.0 Solvent 17 CFO, HC 34 15.2 55.3 29.5 Solvent 1 CFO 35 5.0 86.0 9.0 Solvent 18 PFC 36 5.0 86.0 9.0 Solvent 19 HC 37 5.0 86.0 9.0 Solvent 20 HCFO

(78) TABLE-US-00003 TABLE 3 First fraction Second fraction Concentration (wt %) of 0-, mono- Concentration (wt %) of 0-, mono- and bi-functional species and bi-functional species 0- Mono- Bi- 0- Mono- Bi- functional functional functional functional functional functional Ex. species species species Yield species species species Yield 1 5.4 92.8 1.8 92.2 0.3 5.6 94.1 6.6 2 5.4 93.6 1.0 91.5 0.7 4.2 95.1 7.2 3 5.4 92.4 2.2 92.4 0.1 8.2 91.7 5.8 4 5.3 91.9 2.8 93.0 1.0 7.6 91.4 5.9 5 5.3 91.8 2.9 92.9 1.1 10.1 88.8 5.8 6 5.3 92.5 2.2 92.4 1.4 7.0 91.7 6.2 7 5.3 92.1 2.6 92.8 1.1 7.4 91.5 6.1 8 5.4 94.0 0.6 91.4 0.7 0.5 98.7 7.4 9 5.4 93.9 0.7 91.5 0.7 0.7 98.6 6.7 10 5.3 94.1 0.6 91.3 1.8 0.6 97.6 6.8 11 5.4 94.2 0.4 91.2 0.8 0.7 98.5 7.3 12 5.3 93.5 1.2 91.5 1.8 5.3 93.0 7.1 13 5.4 93.4 1.2 91.6 0.6 5.3 94.1 6.6 14 5.1 91.6 3.3 92.0 3.9 21.6 74.6 6.6 15 5.3 91.3 3.4 92.1 1.5 24.2 74.3 6.7 16 5.4 91.4 3.2 92.0 0.4 23.9 75.7 6.2 17 21.5 77.2 1.3 69.0 0.5 5.6 93.9 29.6 18 21.6 76.8 1.6 69.1 0.2 6.2 93.5 29.8 19 21.5 76.2 2.3 68.0 1.2 9.9 88.9 30.5 20 21.4 76.6 2.0 67.5 1.7 10.1 88.2 30.9 21 21.5 75.8 2.7 67.9 1.3 11.0 87.7 30.9 22 21.4 75.7 2.9 68.3 1.2 10.4 88.4 29.9 23 21.5 76.0 2.8 68.1 1.1 10.2 88.7 30.6 24 21.4 78.1 0.5 70.0 0.1 1.1 98.8 28.3 25 21.4 77.9 0.7 69.8 0.2 2.1 97.7 28.7 26 5.4 93.7 0.9 91.3 0.8 5.2 94.0 7.0 27 5.3 91.4 3.3 93.5 0.7 8.3 91.0 5.3 28 5.3 91.2 3.5 93.6 0.6 10.0 89.4 4.6 29 5.4 93.7 0.9 91.5 0.7 3.1 96.2 6.7 30 5.4 93.9 0.7 91.2 0.9 4.1 95.0 7.1 31 5.4 93.9 0.7 91.1 0.9 5.1 94.0 7.3 32 5.4 94.3 0.3 90.8 0.2 0.6 99.2 8.0 33 5.5 93.7 0.8 88.8 1.4 7.1 91.5 7.4 34 20.2 74.3 5.5 57.2 4.3 17.5 78.2 31.8 35 45.2 51.0 3.8 0.2 40.2 55.4 4.4 0.8 36 53.5 44.1 2.4 0.1 38.5 54.3 7.2 0.2 37 5.2 86.5 8.3 93.0 2.3 79.4 18.3 5.0

(79) As shown in Tables 1 to 3, in Ex. 1 to 34 wherein CFO, HCFO, HFO, cyclic HFC, cyclic CFO or PFK was used as a mobile phase, the yields of fluorinated compounds were high, and in the first fraction, monofunctional species could be separated with high purity, and in the second fraction, bifunctional species could be separated with high purity.

(80) Among them, in Ex. 1 to 13 and 17 to 25 wherein CFO, HCFO, HFO, cyclic HFC or cyclic CFO was used, the purity of monofunctional species in the first fraction was high, and the purity of bifunctional species in the second fraction was high. In Ex. 1, 2, 8 to 13, 17, 18, 24 to 25 wherein CFO, HFO, cyclic HFC or cyclic CFO was used, the purity of monofunctional species in the first fraction was higher, and the purity of bifunctional species in the second fraction was higher. In Ex. 8 to 11, 24 and 25 wherein HFO or cyclic HFC was used, the purity of monofunctional species in the first fraction was further higher, and the purity of bifunctional species in the second fraction was further higher.

(81) In Ex. 33 wherein a mixed solvent of CFO and HC was used, monofunctional species in the first fraction could be separated with high purity, but the yield was lower.

(82) Focusing on the main chain of the fluorinated compound, in Ex. 17 to 25, 32 and 34 wherein fluorinated compounds of the Fomblin type with the main chain being (CF.sub.2O).sub.n.Math.(CF.sub.2CF.sub.2O).sub.m were used, separation capacity for monofunctional species in the first fraction was high, and the separation capacity for bifunctional species in the second fraction was high.

(83) Focusing on OZ(R).sub.n of the fluorinated compound, in Ex. 1 to 25 and 32 to 37 for O(CF.sub.2).sub.3CH.sub.2OH, in Ex. 29 for O(CF.sub.2).sub.3CONHCH.sub.2C(CH.sub.2CHCH.sub.2).sub.3, in Ex. 30 for O(CF.sub.2).sub.3CONH.sub.2, and in Ex. 31 for O(CF.sub.2).sub.3CH.sub.2NHCOC(CH.sub.2CHCH.sub.2).sub.3, the purity of monofunctional species in the first fraction was high, and the purity of bifunctional species in the second fraction was high. In Ex. 34 wherein A is an alkyl group, as compared with Ex. 17 wherein A is a perfluoroalkyl group, the purity and yield of monofunctional species in the first fraction were slightly lower.

(84) This application is a continuation of PCT Application No. PCT/JP2021/033805, filed on Sep. 14, 2021, which is based upon and claims the benefit of priority from Japanese Patent Application No. 2020-155413 filed on Sep. 16, 2020. The contents of those applications are incorporated herein by reference in their entireties.