JPH02215745A - Fluorine-containing alpha,omega-dicarboxylic acid diester and production thereof - Google Patents

Abstract

NEW MATERIAL:A fluorine-containing alpha,omega-dicarboxylic acid diester expressed by formula I (R<1> and R<2> are H, alkyl or aralkyl; R<3> is alkyl or aralkyl; n is a natural number). EXAMPLE:Diethyl 4,4,5,5,6,6,7,7,8,8,9,9-dodecafluoro-1,12-dodecanedioate. USE:Useful as a raw material for fluorine-containing polymers, such as fluorine- contatning polyester or polyamide, having a low refractive index, and oil repellency, chemical heat resistance, etc., and utilizable as a fiber treating material, gas separating material, photoresist, etc., including an optical fiber sheath material. PREPARATION:A fluorine-containing alpha,omega-diiodoalkane expressed by formula II is reacted with an alcoholate expressed by formula III and carbon monoxide in the presence of a group VIII transition metal catalyst and a base to afford the compound expressed by formula I. The compound expressed by formula III is preferably used in an amount in excess of the compound expressed by formula II.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides fluorine-containing α, ω materials which themselves can develop a low refractive index and which can be derived into fluorine-containing polymers such as fluorine-containing polyesters and polyamides. -Relating to a dicarboxylic acid diester and a method for producing the same.

[Conventional technology]

Organic fluorine compounds have a low refractive index, 10% oil resistance, chemical resistance, and heat resistance, so they are used in a wide range of industries, including optical fiber sheath materials, fiber treatment materials, gas separation materials, and photoresists. has been done. Fluorine-containing polymers are also used for similar purposes, but many of these contain fluorine atoms in their polymer side chains, and only a limited number of them contain fluorine atoms in their main chains. The reason for this is that the required polymer raw material is an unknown compound that has not been described in literature. The fluorine-containing α,ω-dicarboxylic acid diester is a compound that has not been described in any literature.

[Problem to be solved by the invention]

The present invention is directed to a novel fluorine-containing α which has a low refractive index by itself and which can be derived into fluorine-containing polymers such as fluorine-containing polyesters and polyamides.

The object of the present invention is to discover ω-dicarboxylic acid diesters and provide a simple and economical method for producing fluorine-containing α,ω-dicarboxylic acid diesters.

(Means for Solving !i!II) The present invention provides the following methods: (wherein n represents a natural number).

(2) In the presence of a Group ■ transition metal catalyst and a base, -a formula % formula % (wherein R' and R1 represent a hydrogen atom, an alkyl group, or an aralkyl group, and n represents a natural number) fluorine-containing α,ω-dicode alkane, and the general formula % formula % () (wherein R3 represents an alkyl group or an aralkyl group,
) A fluorine-containing α,ω-dicarboxylic acid diester represented by the general formula (in the formula, R', R'', R'' and n are the same as above), which is obtained by reacting an alcohol represented by the following with carbon monoxide. Relating to a method of manufacturing.

The compound represented by formula (1) of the present invention can be produced by the production method shown in item 0) of the present invention.

The general formula (II) used as a starting material in the present invention
) is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, such as methyl group, ethyl group, propyl group, 3,3゜3-trifluoropropyl group, butyl group. , hexyl group, cyclohexyl group, octyl group, decyl group, etc. Examples of the aralkyl group include an aralkyl group having 7 to 10 carbon atoms which may have a substituent, such as a benzyl group, a pentafluorobenzyl group, and a phenethyl group.

Fluorine-containing α represented by the general formula (n) in the present invention
, ω-short alkanes are commercially available, but when R1 and R3 are the same in the formula, in the presence of a Group ■ transition metal catalyst, the general formula % formula % () (where n is Same as above, α,ω-jotopolyfluoroalkane represented by ) and the general formula CHm-(:HR'
α represented by the general formula (V) can be easily, safely and advantageously produced by reacting with an olefin represented by (V[) (in which R1 is the same as above) (see Reference Examples below). , ω−
Jotopolyfluoroalkane is commercially available, and the olefin represented by the general formula (Vl) can also be produced industrially. The amount of the olefin to be used is 2 equivalents to an excess amount relative to the α,ω-short perfluoroalkane represented by the general formula (V). Group IV transition metal catalysts that can be used include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum metals, metal salts, metal complex compounds, -
Organometallic complexes using carbon oxide as a ligand, organometallic complexes using a halogen atom as a ligand, organometallic complexes using a tertiary phosphine as a ligand, organometallic complexes using olefins or acetylenes as a ligand. Complexes and their Group I transition metal compounds supported on silica gel or alumina carriers can be used. A suitable catalyst is
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)nisol, dichlorobis(triphenylphosphine)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro(1,3-bis(diphenylphosphino)ethane), dichlorobis(triphenylphosphine)palladium, ) propane] palladium, dichloro[l,4-bis(diphenylphosphino)butane]
Palladium 1. Dichloro(1,1'bis(diphenylphosphino)ferrocene]palladium, dichlorobis(diphenylmethylphosphine)palladium, dichlorobis(triphenylphosphine)platinum, bis(cyclooctadiene>nickel, dichloro(cyclooctadiene)palladium, tetrakis( (triphenylphosphine) nickel, chlorotris (triphenylphosphine) rhodium, chlorotris (triphenylphosphine) iridium, chlorocarbonyl bis (triphenylphosphine)
Examples include rhodium, chlorocarbonylbis(triphenylphosphine)iridium, tetrakis(triphenylphosphine)palladium, and tetrakis(triphenylphosphine)platinum. The amount of the Group (IV) transition metal catalyst to be used can be appropriately selected from the range of 1/10,000 to 1/2 equivalent relative to the α,ω-short perfluoroalkane represented by the general formula (V).
A range of from 1/3 to 1/3 is preferred, and if desired, amines such as pyridine, triethylamine, diethylamine, and ethanolamine may be added as cocatalysts. The reaction proceeds smoothly at 0°C to 150°C. Note that the reaction can be carried out without a solvent, but if desired, a solvent that does not participate in the reaction may be used.

The alcohol represented by the general formula (III) used in the present invention includes methanol, ethanol, linear or cyclic primary or secondary propatools which may be branched, butanols, pentanols, and hexanols, benzyl alcohol, phenethyl alcohol and the like. The amount of the alcohol represented by the general formula (III) is usually in excess of the compound represented by the general formula (■), and it may also serve as a solvent.

The present invention is carried out in a -carbon oxide atmosphere, which 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 atmospheres or less, but if desired, High pressure may be used.

The essential condition of the present invention is that it is carried out in the presence of a Group Ⅰ transition metal catalyst. Group Ⅰ transition metal catalysts that can be used include iron, cobalt, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum metals, metal salts, gold rsH compounds, and organic Metal complexes, organometallic complexes with a halogen atom as a ligand, organometallic complexes with a tertiary phosphine as a ligand, organometallic complexes with an olefin or acetylene as a ligand, and group IV transitions thereof A metal compound supported on a 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, baltic 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)fu10cene]
Palladium, dichlorobis(diphenylmethylphosphine)palladium, dichlorobis(triphenylphosphine)platinum, bis(dichlorooctadiene)nickel, dichloro(cyclooctadiene)palladium, tetrakis(triphenylphosphine)nickel, chlorotris(
triphenylphosphine) rhodium, chlorotris(triphenylphosphine) iridium, chlorocarbonylbis(triphenylphosphine) rhodium, chlorocarbonylbis(triphenylphosphine)iridium, tetrakis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)platinum, Examples include dichlorotris(triphenylphosphine)ruthenium. The amount of the Group (IV) transition metal catalyst to be used can be appropriately selected from the range of 1/10,000 to 1/2 equivalent to the fluorine-containing α,ω-short alkane represented by the general formula (n). ) 500 to 1/3 is preferred.

The present invention requires that the reaction be carried out in the presence of a base. Examples of the base include inorganic salts such as hydroxides, carbonates, fluorides, and oxides of alkali metals or alkaline earth metals, and organic bases such as triethylamine and pyridine. The amount of base used is preferably 1 equivalent or more relative to the compound represented by the general formula (1)).

In carrying out the present invention, solvents that do not participate in the reaction can be used. Examples of these include aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, cyclooctane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, acetone, chloroform, ether, tetrahydrofuran, dioxane, t
Examples include polar solvents such as -butyl alcohol and [-amyl alcohol.

When the solvent forms two liquid phases, or when a base is added to the solvent used, I!
If it is soluble, a phase transfer catalyst such as a quaternary ammonium salt may be added if desired.

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

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

Example 1 CHgCIlml CHgC)lxcOOBL 1.10-
Short-3, 3, 4, 4, 5, 5゜6.6.7,7,
8.8-Dodecafluorodecane (0,153g, 0
．． 25 mm o l ), Cot(Co)s(8,
5q, 0.025mmo 1), KF (58w.

1mmo1) and [! Add tO■ (1 ml) and Go(
50 atm) and reacted at 100°C for 24 hours. Nonane (201) 1,0,1) 2mm as internal standard
As a result of adding o l) and quantifying by gas chromatography, the results were 4,4,5,5.6.6,7,7,8,8゜9
．． It was found that 72% diethyl 9-dodecafluoro-1,12-dodecanoate was produced.

The product was isolated and purified by silica gel column chromatography.

^na1. Ca1cd for C+aH+aF+g
O*.

CF 38.26. Hj 3.61found C
: 38.15. H: 3.54I R(n a
a t) 1738cm-' (shi c-o)' H
-NMR (CDCIs, TMS) 61.26
(t.

J-7Hz, 6H), 2.1-2.9 (m
.

8H), 4.18 (q, J=7Hz,
4H).

"F-NMR (CDCIs, TMS) δ-1)5
,2(br, 4F), -122,4(br.

4F), -124,1 (br, 4F).

Mas s m/e (tel, lnt,)
502 (M”.

16), 457 (100), 429 (99
), 402 (21), 129 (26),
123 (22), 77 (24)55
(48), 45 (20), 29 (93).

Examples 2 to 5 The reaction was carried out under the same conditions as in Example 1 except for the catalyst and base used, and the reaction was conducted at 4, 4, 5, 5.6, 6°? , 7, 8.
Table 1 shows the types and amounts of catalysts and bases used in the reaction to obtain diethyl 8.9.9-dodecafluoro-1,12-dodecanoate, as well as the yield.

Example 6 Table 1 Example catalyst (-kasumi o1) Co * (Co) @ (0,025) (PhlP)
tPdclt(0,025)(PhlP)*PdCIg
(0,025) Rh & (Co) + 6 (0,0
04) Base yield (+s■01) (%) at3N (0,5) KF (1) atss (0,5) atsM (0,5) In a 10 ml stainless steel autoclave, 1.8-short-3, 3,4,4,5,5,6゜6-octafluorooctane (128■, 0.25 mmol), 6
oz(Co)* (8.5w, 0.0025mmo
l), KF (58w, 1mmo I), and RtO
Add H (1 ml) and seal CO (50a ts).
The reaction was carried out at 100°C for 24 hours. Add tetradecane (20 μj, 0.077 mmol) as an internal standard,
As a result of quantitative determination by gas chromatography, it was 4°4.
5.5,6.6.7.7-octafluoro-1,10-
Diethyl decanoate was produced in 64% yield.

The product was isolated and purified by silica gel column chromatography. Ca1cd for C+
aH+5FsO*.

C: 41.80. H: 4.5+ found C: 41.66, H: 4.58J
R(neat) 1738cx-'(+'c-o)
'H-NMR (CDC13, TMS) 61.26
(t.

J-IHz, 6H), 2.1-2.95 (m.

8H), 4.18 (Q, J-7Hz, 4H).

"F NMR (CDCh8 MS) δ -1
) 3,9 (br, 4F), -122,7 (br.

4F).

Mas s m/e (ral, lnt,)
402 (M”.

6), 357 (60), 329 (31) 284
(5), 55 (53), 45 (16), 29 (1
00).

Examples 7 to 1) The reaction was carried out under the same conditions as in Example 6 except for the catalyst and base used in the reaction, and the reaction conditions were 4, 4.5, 5°, 6.6, 7.7
Table 2 shows the types and amounts of the catalyst and base used in the reaction to obtain diethyl -octafluoro-1,10-decanoate, as well as the yield.

Table 2 Example catalyst (amol) Cow (CO) * (0,025) (PhsP)tPdcIg (0,025) (PbsP)
1Pdcl 1 (0,025)12h4(Co)l
&(0,004) 'Rh table (Co)l&(0,004) Base (Steel 5ol) Yield (%) at! N(0,5) MP(1) Etsll(0,5) KP(1) EtJ(0,5) Example 12 In a 30ml stainless steel autoclave, 1,6-diiodo3.3,4.4-tetra Fluorohexane (0
,41g, 1mmo +>, Cow(Go)s
(34w, 0.1mm o l), F (0
, 236g.

4 mmo I) and IlttOH (4 ml) were added, Co (50 ats) was sealed, and the mixture was reacted at 100° C. for 24 hours. After completion of 7 reactions, extraction was performed with ether, and after washing with water, the ether layer was dried with Mg5Oa. The ether was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (
As a result of isolation and purification using (developing solvent: chloroform), 4.4
, 5.5-tetrafluoro-1,8-octanioate diethyl was obtained in a yield of 0.233 g (77%).

^na1. Caled for C++*H+5F40
*.

C: 47.68. Hj 6.00°found C: 47.40. H: 6.02゜IR(ne at) 1740aa-' (
1'c-o)' H-NMR (CDC1i, TMS
) 61.26 (tJ-IHz, 6H), 2.0-2
．． 8 (m8H), 4.18 (q, J=IHz, 4H
).

"F NMR (CDCIs, TMS) δ-137
,7 (m, 4F) Ma s s m/e (tel, int,)
302 (M”.

8), 257 (47), 229 (15).

209 (56), 55 (60), 29 (100).

Example 13 Cog (Co) m of Example 12 (PhsP) t
PdcIg (70■.

0.1 mmo I) and KF [! tsN (0,28
Example 12 except that ml, 2 mmol)
The reaction was carried out under the same conditions. As a result, diethyl 4.4,5.5-tetrafluoro-It s-octanioate was obtained with a yield of 86%.

Example 14 cns C1
+.

In a 50m1 stainless steel autoclave, 2.1)-
Short-4, 4, 5, 5, 6, 67, 7, 8, 8, 9
,9-dodecafluorododecane (0,638g+1
mmo I), (PhsP)zPdclm (70w,
0.1 mmol), KW (0,232 g, 4 mrn
ol), and [! Add tOH (4 ml) and add co(5 ml).
The 0 reaction mixture was sealed with 0a t■) and reacted at 100°C for 24 hours, and then extracted with ether, washed with water, and dried over MgSO4. After distilling off the solvent under reduced pressure, the residue was subjected to silica gel column chromatography (developing solvent: chloroform).
As a result of isolation and purification, 2.1)-dimethyl-4,4,5
, 5,6,6,7,7,8゜8.9.9-dodecafluoro-1,12-dodecanoic acid diethyl 0.408 g
(77%) yield.

Anal, Ca1cd for CraH*zF+z
Oa.

CF 40.77, H! 4.1B.

found C+ 40.87. H: 4.10°IR (neat) 1740cs day (W c-o)
' H-N M R (CDC1s, TMS) δ1.
25 (5J=7Hz, 6H), 1.30
(d, J-7Hz, 6H), 1.85-3.1 (m
, 6H).

4.18 (q, J-IR34H).

”F -N M R (CDCIs, TMS) δ-1
)5,3(br, 4F), 123.6(br
.

4F), -125,7 (br, 4F).

Ma s s m/e (rel, lnt,)
530 (M”10), 485 (26),
457 (30).

429 (21), 91 (28), 73
(15), 47 (62), 45 (1)
)29(100).

Examples 15 to 18 Performed in the same manner as Example 14, 2.1)-dimethyl = 4.4
,5.5,6,6,7.7.8,8,9゜2,1)-Short-4,4, used in the 6 reaction to obtain diethyl 9-dodecafluoro-1,12-dodecanoate 5, 5, 6, 6
, 7,7,8,8,9° The amount of 9-dodecafluorododecane, the type and amount of the catalyst and base used, the amount of solvent, and the yield are shown in Table 3.

Example 19 CHI C
H3 Example 14-2,1)-Short-4,4,5゜5
．． 6.6.7,7,8,8,9.9-dodecafluorododecane to 2.9-short-4,4,5°5.6,6.
7.7-octafluorodecane (0,538 g, 1 mm
The reaction was carried out under the same conditions as in Example 14, except that the reaction conditions were changed to (o l). As a result, 2,9-dimethyl-4,4,5,
Diethyl 5,6,6,7°7-octafluoro-1,10-decanoate was obtained in a yield of 0.348 g (81%).

Anal, Ca! cd for C+iHtgF++
Oe.

C: 44.66, H: 5.15°found C=44.38. H: 5.1)゜IR(neat) 174Qcs+-'(shico
)” H-N M R (CIICIs, TMS) 6
1.25 (t.

J=7Hz, 6H), 1.30 (d, J-
7Hz, 6H), 1.9-3.1 (m, 6H).

4.17 (Q, J-IHz, 4H).

'''F NMR (CDCb, CFCIs)
δ-1)9,9(br,4F),-126,1(b
r.

4F).

M ass m/e (tel, lnt,)
430 (M'.

14), 385 (36), 357 (36)26
9 (24), 91 (35), 47 (34),
29 (100).

Examples 20 to 23 Performed in the same manner as Example 19, 2,9-dimethyl-4,4,
5,5,6,6,7,7-octafluoro-1,1O-
Amount of 2,9-short-4,4,5,5,6゜6.7.7-octafluorodecane used in 9 reactions to obtain diethyl decanoate, type and amount of catalyst and base used, solvent The amounts and yields are shown in Table 4.

Reference Example 1 The measured values of the refractive index of the fluorine-containing α,ω-diester obtained in the present invention are summarized in Table 5. For comparison, the dicarboxylic acid obtained in the present invention and the number of carbon atoms in the main chain are The refractive index values of equivalent hydrocarbon diesters are also listed. The refractive index was measured using a refractometer manufactured by ATAGO.

Table refractive index reference example 2 + (CFx) + I + CH□-C1)゜ICHt
In a CHg(Ch)oCLC1ldlQml stainless steel autoclave, 1,4-short perfluorobutane (180μj, 1.0mmol) and iron pentacarbonyl (14uj.

Q, 1 mmol), ethanolamine (12 μm5
Ether was added to the reaction mixture, which was stirred at 100°C for 3 hours with ethylene (10 atm) added, and octane was added as a standard reaction mixture. When GLC was measured, it was found that 1.8-short-3゜3.4,4.5
, 5,6.6-octafluorooctane was produced in a yield of 78%. Hydrochloric acid was added to the 0 reaction mixture, the ether layer was separated, the ether was distilled off, and 1 was recrystallized with methanol. .8-Short-3, 3, 4, 4, 5,
5,6°6-octafluorooctane was isolated and purified.

IR (Br) 1)95. 1)? 1. 1) 12
゜1064, 722. 512cm-''HN M
R (CDCIs, TMS) 62.1-3.0 (
bm, 4H), 3.0-3.6 (bm.

4H).

” F N M R (CDCh, CFCIs)
δ-1)(m, 4F), 123.0
(m.

Mas s m/e (rel, Int,
) 51085), 383 (55),
14177 (100), 65 (72).

(25), 47 (21), 2827 (35
).

Ca1cd for C@Ha F m It
.

C: 18.84. H: 1.58゜foun
d C: l 8.76, H: 1.42° 4.4 4F).

(M’″.

(67).

(25).

Aaal.

Reference Examples 3 to 17 The amounts of 1,4-short perfluorobutane and ethylene used in the 0 reaction conducted in the same manner as Reference Example 2, the type and amount of the catalyst and amine used, the reaction temperature, reaction time, and yield. It is shown in Table 6.

Reference example 18! (CFg)hr + CHI ”CHH--ICH
wCHs(Ch)icHtcH*150m! 1,6-shorter fluorohexane (2,5
8g, 4.46mmol) iron dodecacarbonyl (16
3■, 0.32 mmol) and ethylene (10 at
s) and reacted at 80°C for 5 hours. Hydrochloric acid was added to the reaction mixture, extracted with ether, and recrystallized with methanol to obtain 1.10-short-3,3,4,4
, 5°5.6,6.7,7,8.8-dodecafluorodecane (2.65 g) was obtained with a yield of 93%.

' HN M R (CDCIs, TMS) δ2.3
~3.1 (m, 4H), 3.1~3.4 (
m, 4H).

"F-NMR (CDCII, CFCl2) δ-1)
4,2 (m, 4F), -122,1 (m, 4F).

-123,0 (m, 4F).

IR (KBr) 1215.1) 70°1) 34,
1062. 688 Ma s s m/e (rel, lnt,
) 61)00), 463 (24),
1 (46), 77 (65), 6551
(20), 27 (19).

Reference example 19 512cm-' 0 (M”.

(43).

+(CFg)4I+ CHt Proverb CHCHsChi
s C1C1 1.4-short perfluorobutane (4.7 g, 10.36 mmc) in a 1s50 stainless steel autoclave.
l), Fas(Co)+x(0.24g, 0.48m
mol) and propylene (1240rnl, 55.0rnl).
After sealing in 4 mmol) and reacting at 100° C. for 24 hours, an aqueous sodium thiosulfate solution was added to the reaction mixture, followed by extraction with ether. The ether layer was washed with water and then dried with Mg5O*. 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-short-4,4,5
,5,6,6,7゜7-octafluorodecane 3.4
Obtained in a yield of 5g (62%).

mp 35.0~35.5℃ Anal, Calcd for C+*H+sFs
I! .

c: 22.33. H: 2.25°found C: 22.46. H: 2.22°IR (KBr) 1365, 1268°1208.
1)65,1)18゜1032.868,715.502cm-''H-NM
R(CDCI□Tas) 62.04 (d.

J-IHz, 6H), 2.2-3.30 (m.

4H), 4.45 (tq, J-1and7Hz, 2
H), 'y'F-NMR(C
OCh, CFCIs) δ-1) 4,2 (m, 4F)
, -124,0 (m, 4F).

Mass m/e (tel, Int,)
538 (M”.

2), 410 (4), 283 (29)
155 (12), 91 (22), 77
(1)), 65 (18), 47 (10
0).

41(25).

Reference example 20! (CFx)bl + CHm -CHCHz
□→CI1. C1l.

1,4-short perfluorobutane of Reference Example 19
．． The reaction was carried out in the same manner as in Reference Example 19, except that 6-short perfluorohexane was used.

As a result, 2,1)-short-4,4,5,5゜6.
6.7.7,8,8,9.9-dodecafluorododecane was obtained with a yield of 89%.

rfl 53℃ Anal, Calcd for C+tHr*F
lt Is.

C: 22.59. H: 1.90゜foun
dC: 22.22. H: 1.74゜I
R(KBr) 1455. 1368°1272,
1202. 1) 70°1) 40, 1019. 689. 660°508 Country-1' H-NMR (CDCIs, TMS) 62.
04 (d.

J=7Hz, 6H), 2.30~3.30 (m
.

4H), 4.45 (tq, J=7 a
nd7Hz, 2H).

”F-NMR(CDCIslCFCIs)
δ-1)4,1(m, 4F), -122,1
(m, 4F).

-124,0 (m, 4F).

Ma ss m/e (tel, int,
) 63 B (M”.

1), 384 (15), 91 (9).

65 (12), 47 (100), 43
(41).

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are each independently a hydrogen atom,
It represents an alkyl group or an aralkyl group, R^3 represents an alkyl group or an aralkyl group, and n represents a natural number. ) Fluorine-containing α,ω-dicarboxylic acid diester. (2) In the presence of a Group VIII transition metal catalyst and a base, general formula ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 each independently represent a hydrogen atom,
It represents an alkyl group or an aralkyl group, and n represents a natural number. ) and an alcohol represented by the general formula R^3OH (wherein R^3 represents an alkyl group or an aralkyl group) with carbon monoxide. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2, R^3 and n are the same as above.) Production method.