JPH02289535A - Fluorine-containing alpha,omega-bifunctional compound - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R<1> and R<2> are H, alkyl or aralkyl; n is a natural number; X is -COY (Y is halogen or N3) or -NCO]. EXAMPLE:4,4,5,5,6,6,7,7,8,8,9,9-Dodecafluoro-1,12-dodecanedioic acid chloride. USE:A raw material for fluorine-containing polymers. The compound is employed for the preparation of polyesters, polyamides, etc., having excellent chemical resistance and durability and containing fluorine atoms in the main chain thereof and also employed for the preparation of fluorine-containing polyurethanes useful for antithrombogenic materials. PREPARATION:An alpha,omega-diiodopolyfluoroalkane of formula II is reacted with an olefin of formula V or VI in the presence of a VIII group transition metal catalyst to prepare a compound of formula III, which is reacted with water, CO and a base in the presence of a VIII group transition metal catalyst to prepare a compound of formula IV. The compound of formula IV is reacted with a halogenating agent to provide the compound of formula I wherein X is COX and Y is halogen.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides fluorine-containing α useful as a raw material for fluorine-containing polymers.
, relating to ω-bifunctional compounds.

The fluorine-containing polymer has tn water ta oil resistance, chemical resistance, and light resistance (
M16, which is widely used in fiber treatment agents, optical fiber sheathing agents, gas permeable membranes, photoresists, etc. (e.g. R&D Revo-), is the most advanced application of fluorine compounds due to its weatherability, heat resistance, and low refractive properties. Technology, CMC (1981))
However, many of these contain fluorine atoms in their polymer side chains, and only a limited number of them contain fluorine atoms in their polymer main chains. This is due to the lack of a manufacturing method for polymer raw materials.

The fluorine-containing α,ω-difunctional compound provided by the present invention can be derived into polyesters, polyamides, etc. containing fluorine atoms in the main chain, and the fluorine-containing α,ω-diisocyanate of the present invention has anti-oxidant properties. It is well known in the art that fluorine-containing polyurethanes can be produced that can be used as thrombotic agents (M, Kat.

et al., Progress In Artificial
Organs+2+ 858 (1983), )
.

[Conventional technology]

Conventionally, as the fluorine-containing α,ω-bifunctional compound of the present invention, one having one methylene chain between each functional group and a difluoromethylene group has been known (T, Takakur et al.
a et al., J. Fluorine Chem, +41
+173 (1988), ), but this compound easily decomposes under basic conditions and has the disadvantage of poor chemical resistance, so it not only requires care when handling, but also has poor weather resistance and durability. It is a well-known fact among those skilled in the art that there are disadvantages in the sex. Furthermore, the dicarboxylic acid itself, which is the raw material, not only has poor chemical resistance, but also requires multiple steps to synthesize.

[Problem to be solved by the invention]

The present invention solves the above-mentioned drawbacks of the prior art, and discovers a new fluorine-containing α,ω-bifunctional compound that has excellent chemical resistance and durability, and can reduce the manufacturing process.
The present invention has been completed.

[Means to solve the problem]

The present invention is based on the formula (where RI and R1 each independently represent a hydrogen atom, an alkyl group, or an aralkyl group, n is a natural number, and
is -COY or -NGO, Y is a halogen atom or N, and relates to a fluorine-containing α,ω-bifunctional compound.

The compound represented by formula (+) of the present invention can be produced by the following steps.

1 (Ch), I (n
)↓ [First step] ↓ [Second step] C0OHC00I+ ↓ [Third step] ↓ (Fourth step) Aralkyl group having 7 to 10 carbon atoms, for example, benzyl group,
Examples include pentafluorobenzyl group and phenethyl group.

[First step]

↓ [Fifth Step] [In the formula, R'+R''+n is the same as above, and V'' is a halogen atom. ] The alkyl group in the present invention is preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, such as a methyl group, an ethyl group, a propyl group, a 3°3.3-)lifluoropropyl group, Examples include butyl group, hexyl group, cyclohexyl group, octyl group, and decyl group.

As the aralkyl group, the fluorine-containing α, ω represented by the formula (■) obtained in this step, which may have a substituent, is
- Although short alkanes are available industrially,
In the presence of a Group II transition metal catalyst, - an α,ω-jotopolyfluoroalkane represented by formula (II) and a general formula % formula % () and - formula CH, “CHR” (Vl)
It can be easily, safely and advantageously produced by reacting with an olefin represented by the formula (wherein R1 and Rs are the same as above). The α,ω-jotopolyfluoroalkane represented by the above-mentioned formula (II) is commercially available, and the olefins represented by the above-mentioned formulas (V) and (Vl) are also industrially available.

The amount of each olefin used is α shown in the formula (■) above.
, 1 equivalent to or in excess of ω-short perfluoroalkane. Examples of Group Ⅰ transition metal catalysts that can be used include iron, Ruthenium J4, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum metals, metal salts, metal complex compounds, and carbon oxide as a ligand. Organometallic complexes, organometallic complexes having a halogen atom as a ligand, organometallic complexes having a tertiary phosphine as a ligand,
Organometallic complexes having olefins or acetylenes as ligands and Group I transition metal compounds thereof supported on silica gel or alumina carriers can be used. Suitable catalysts include iron carbonyl, ruthenium carbonyl, osmium carbonyl, cobalt carbonyl, rhodium carbonyl, nickel carbonyl,
Iron chloride, cobalt chloride, ruthenium chloride, rhodium chloride, nickel chloride, palladium chloride, platinum chloride, dichlorobis(triphenylphosphine)nickel, dichlorobis(triphenylphosphine)palladium, dichloro[1]
, 2-bis(diphenylphosphino)ethane]palladium, dichloro(13-bis(diphenylphosphino)propane)palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro[11
′Bis(biphenylphosphino)ferrocene]palladium, dichlorobis(diphenylmethylphosphine)palladium, dichlorobis(triphenylphosphine)platinum, bis(cyclooctadiene)nickel, dichloro(cyclooctadiene)palladium, tetrakis(triphenylphosphine)nickel , chlorotris(triphenylphosphine) rhodium, chlorotris(triphenylphosphine) iridium, chlorocarbonylbis(triphenylphosphine)rhodium, chlorocarbonylbis(triphenylphosphine)iridium, tetrakis(
Examples include triphenylphosphine)palladium and tetrakis(triphenylphosphine)platinum. The amount of the Group Ⅰ transition metal catalyst to be used is given by the above-mentioned formula (El).
The equivalent range can be appropriately selected from 1/10,000 to 1/2 equivalent to the α, ω short perfluoroalkane represented by, but the range of 11,500 to 1/3 is preferable. It is also possible to add amines such as diethylamine, diethylamine, and ethanolamine.

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.

[Second process]

ω-Short alkane and water, -carbon oxide and base as part
By reacting in the presence of a group transition metal catalyst, a fluorine-containing α,ω dicarboxylic acid represented by formula (IV) is synthesized.

In this step, the amount of water used is usually in excess of the compound represented by formula (11) above, and 2
It is desirable to use the amount approximately 200 times to 200 times.

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

It is essential that this step be carried out in the presence of a Group Ⅰ transition metal catalyst. Examples of Group Ⅰ transition metal catalysts that can be used include iron, cobalt, ruthenium, osmium, rhodium, and iridium.
Fluorine-containing α expressed as

metals, metal salts, metal complexes of kel, palladium, and platinum, -organometallic complexes with carbon oxide as a ligand, organometallic complexes with a halogen atom as a ligand, organic compounds with a tertiary phosphine as a ligand Organometallic complexes having gold 171EIW, olefins or acetylenes as ligands, and these Group I transition metal compounds supported on silica gel or alumina carriers can be used. Suitable catalysts include iron carbonyl, ruthenium carbonyl,
A Sumilum carbonyl, cobalt carbonyl, rhodium carbonyl, nickel carbonyl, iron chloride, cobalt chloride, ruthenium chloride, rhodium chloride, nickel chloride, palladium chloride, platinum chloride, dichlorobis(triphenylphosphine)nickel, dichlorobis(triphenylphosphine) Palladium, dichloro[1,2-bis(diphenylphosphino)ethane] palladium, di,chloro[1
,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)butane]palladium, dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium, dichlorobis(diphenylmethyl phosphine) palladium, dichlorobis(triphenylphosphine) platinum, bis(cyclooctadiene) nickel, dichloro(cyclooctadiene) palladium, tetrakis(triphenylphosphine) nickel, chlorotris(triphenylphosphine) rhodium, chlorotris(triphenylphosphine) Examples include iridium, chlorocarbonylbis(triphenylphosphine)rhodium, chlorocarbonylbis(triphenylphosphine)iridium, tetrakis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)platinum, dichlorotris(triphenylphosphine)ruthenium, etc. The amount of Group Ⅰ transition metal catalyst to be used is 1/1 of the fluorine-containing α,ω-short alkane represented by formula (III) above.
The range of 0,000 to 1/2 equivalent can be selected as appropriate;
A range of 1500 to 1/3 is preferred.

An essential condition for this step is that it be performed in the presence of a base. Examples of the base include inorganic salts such as alkali metal or alkaline earth metal hydroxides, carbonates, fluorides, and oxides, 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 formula (fil) above.

In carrying out this step, a solvent that does 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
-Polar solvents such as butyl alcohol and t-amyl alcohol can be mentioned.

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

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

[Third step]

In this step, - containing /element α represented by the above-mentioned formula (IV)
, ω-dicarboxylic acid is reacted with a halogenating agent to obtain a fluorine-containing α represented by the above formula (la).

This is to produce ω-diacid halide. As the halogenating agent that can be used, those capable of converting ordinary carboxylic acids into acid halides can be used. For example, thionyl chloride, phosphorus pentachloride, silicon tetrachloride, oxalyl halide, phosphorus tribromide, etc. are preferably used. Can be used.

The amount used is from 2 equivalents to an excess of the compound represented by formula (■) above.The reaction proceeds without a solvent, but
If desired, a solvent that does not participate in the reaction may be used.

The reaction proceeds smoothly in the temperature range of room temperature to 150°C.

The amount of base used is approximately 2 to 100%.

The reaction is preferably carried out in a solvent, and a solvent that does not participate in the reaction, such as a hydrocarbon solvent or an ether solvent, can be used.

The reaction proceeds smoothly at 8°C to room temperature.

[Fourth step]

[Fifth step] In this step, the fluorine-containing α represented by the above-mentioned formula (I a)
, reacting an ω-diacid halide with an alkali metal salt of azide water XalF or with hydrazoic acid in the presence of a base,
A fluorine-containing α,ω-diacid acid represented by the above formula (Ib) is synthesized.

The amount of alkali metal salt of hydrazoic acid or hydrazoic acid to be used is 2 for the compound represented by formula (I a) above.
Use equivalent to excess amount.

As the base, an organic base such as pyridine or triethylamine or an inorganic base such as potassium carbonate is used as appropriate in this step.
The fluorine-containing α,ω-diacid acid represented by the formula (Ib) is subjected to Curtlus rearrangement to synthesize the fluorine-containing α,ω-diisocyanate represented by the formula (Ic).

The reaction is preferably carried out in a solvent, and a solvent that does not participate in the reaction, such as a hydrocarbon solvent or an ether solvent, can be used.

The reaction proceeds smoothly at 50-150°C.

In addition, the fluorine-containing α, ω represented by the above-mentioned formula (IC)
If the purpose is to synthesize diisocyanate, the above formulas (1a) and (Ib) obtained in the third step and the fourth step
It is better to carry out the present invention without isolating the
It is preferable in terms of ease of operation and ease of operation.

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.

Reference example 1 1(CFz)4I + CHx=CHtICHgC
Hx (CPx) 4CH*CHd 10ml stainless steel autoclave, 1.4 siotoperfluorobutane (
180μffi, 1.0mmol), iron pentacarbonyl (14μlO0100l l), ethanolamine (12μm!.

Ether was added to the reaction mixture, which was stirred at 100°C for 3 hours, and octane was added as a standard substance. When GLC was measured, 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 low octafluorooctane was isolated and purified.

IR(KBr) 1195.11?1,1112,1
064,722,512cm-''H-NMR (CDC
1s, TMS) 62.1~3.0(b(4H)
3.0-3.6 (bm, 4) 1).

"F-NMR (CDCIs, CFCIs) δ-11
4,4(m, 4F) -123,0(s, 4F).

Mass a/e (tel, lnt,) 510 (M”
, 85), 383 (55), 141 (67), ? ? (1
00), 65 (72), 51 (25), 47 (21)
2B (25), 27 (35).

^na1. Ca1cd for CC51lsFs1
°C: 18.84. H: 1.58°found
C: 1B, 76, H: 1.42゜mp 93.5℃.

Reference example 2 1 (CF if + CH!-CHmICHtCH
t(CFt)icH*cHm 1.6-diiodoperfluorohexane (2,58g
, 4.46 mmol) iron dodecacarbonyl (163 g
1,0.32 mmol) and ethylene (10 at-
) was sealed 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,
5.6.6,7.7,8.8-dodecafluorodecane (2.65 g) was obtained in a yield of 93%.

'H-NMR (CDCIs, TMS) δ 2.3~
3.1 (m, 4H), 3.1-3.4 (m, 4H).

19P-NMR (CDC1slCPC1a) δ
-114,2 (Mongolia, 4F), -122,1 (m, 4F)
, -123,0 (s, 4F).

IR (KBr) 1215.1170, 1134.1
062.688,512 cm-'Mass m/
e(rel, int,) 610 (M”, 100), 46
3 (24), 141 (46),? ? (65), 65(4
3), 5N20), 27(19).

Anal, Ca1cd for C+JJ+t1g.

C: 19.69. H: 1.32°found
C: 19.94. H: 1.33°sp
91℃.

Reference Example 3 1(Ch)41+C%-It-CHCHsC1,CH3 1.4-short perfluorobutane (4.7 g, 10.36 mm) was placed in a 50 ml stainless steel autoclave.
o l), Fe5(Co)+x(0.24g, 0.4
8mmol) and propylene (1240ml1.55
．． After enclosing 4 mmol, a sodium thiosulfate aqueous solution was added to the reaction mixture, which was reacted at 100° C. for 24 hours, and extracted with ether. After washing the ether layer with water, M g S
It was dried on Oa. After distilling off the fJ medium 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 was obtained in a yield of 3.45 g (62%).

mp　　　　　35.0-35.5℃.

Anal, Ca1cd for C+J+*F
s1m.

C: 22.33. If: 2.25°found
(: 22.46.H: 2.22゜IR(KBr)
1365.1268.1208.1165,1118
,1032゜868.715,502 c--1'H-NMR (CDC1s4MS) δ 2.04
(d, J-7Hz, 611), 2.2 ~ 3.30 (m
, 4H), 4.45(tq, J-7and 7Hz, 2
B).

"F-NMR (CDC1s, CFCls) δ-1
14.2 (m, 4F), 424.0 (m, 4F).

Mass m/e (tel, lnt,) 538 (M”
, 2), 410 (4), 283 (29), 155 (12
), 91(22), ? ? (11), 65(18).

47 (100), 41 (25).

Reference example 4 1(CFg)if+CH proverb-CIlCH3 Reference example 3-1
．． The reaction was carried out in the same manner as in Reference Example 3, except that 4-short perfluorobutane was changed to 1,6-short perfluorohexane. As a result, 2.11-day-do4.
4. 5. 5. 6゜6.7,7.8.8.9.9-
Dodecafluorododecane was obtained with a yield of 89%.

v+p　　　53℃.

Anal, Ca1cd for C eyes H+*F+*I
g.

C: 22.59. II: 1.90found C
: 22.22. H: 1.74°IR (KBr)
1455, 1368, 1272, 1202.1170.
1140.1019689.660,508 am-''H-NMR (CDCIS, TMS) δ2.04(
d, J-7Hz, 6H), 2.30-3.30 (m, 4
H), 4.45 (tq, J-7 and 7) 12.2
H).

” F-NMR (CDCIS, CFCh) δ-11
4,1 (m, 4F), -122,1 (■, 4F), -1
24,0 (■, 4F).

Mass m/e (tel, lnt,) 638 (M
”, 1), 384 (15), 91 (9) 65 (12),
47 (100), 43 (41).

Reference example 5 In a 200m1 stainless steel autoclave, 1.1O
-Short-3, 3, 4, 4, 5, 56, 6, 7, 7,
8,8-dodecafluorodecane (14,65g, 24m
mo I), C0x(CO)s (1,63g, 4.7
7 mmo 1), KF (5.6 g 96 mmo I), water (8.8 m 1.488 mmo I), and t-BuO
H (80 ml) was added, Co (50 atm) was sealed, and the mixture was reacted at 80°C for 48 hours. Concentrated hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ether. The ether layer was washed with water and then dried over magnesium sulfate. After distilling off the ether under reduced pressure, the residue was recrystallized from ether-hexane.
．． 10.09 g of 4,5,5,6°6.7.7.8.8.9.9-dodecafluoro-1,12-dodecanedioic acid
(94%) yield as a white powder.

wp　　182℃.

IR (XBr) 3300~2800cm-'(ν.-
,)1715cm”(ν.,.) Anal, Ca1cd for C+xll+aF+
xO4°C: 32.30. II: 2.26゜fo
und C: 32.44. Old 2.29°H-NMR (
d, -acetone, TMS) 62.4 (a, 4H
), 2.7 (m, 4H).

9.0 (br, 211).

'F-NMR (da-acetone, cFcls)
δ-114,1 (br, 4F).

-121,3 (br, 4F), -123,2 (br, 4
F).

Mass m/e (rel, Int,) 429 (M”
-17,20), 402(41).

139 (52), 131 (37), 123
(33), 109 (47), 103(10
0), 77 (62), 59 (64),
55 (80), 47 (44).

45 (40).

Reference Example 6 1,10-Short-3,3,4°4.5 of Reference Example 5.
5.6,6.7,7,8.8-dodecafluorodecane to 1.8-short-3,3,4°4,5. 5. 6
．． 6-octafluorooctane (12,24g, 24
The reaction was carried out under the same conditions as in Reference Example 5, except that the amount was changed to 44, 5. 5. 6. 6. 7
．． 7-octafufluoro1.10-deca7dioic acid 6.6
Obtained as a white powder with a yield of 5 g (80%) 17).

mp　　　　　　187-187.5　℃.

IR (KBr) 3300~2800cm-'(SiO-
N) 1720 cm-'(1' c-o) Anal, Ca1cd for C+J+JsOa.

C: 34.7G, H: 2.91°found
C: 34.75. H: 2.75゜'If-N
MR (da-acetone, TMS) 62.51
(m, 4H), 2.66 (m.

4H), 11.0 (br, 2H).

11F-NMR (dh-acetone, CFCIs)
δ-114,4 (br, 4F).

-123,3 (br, 4F).

Mass m/e(rel, Int,)329(1
'l''-17, 11), 302(8).

123 (23), 109 (31), 103 (86),?
? (56), 73 (41), 59 (4B), 55 (10
0), 47 (51), 45 (41).

Reference Example 7 In a 29 ml stainless steel autoclave, 1,6-diiodo 3,3,4,4-tetrafluorohexane (0
,41g,1mmo+),C(h(CO)s(33
w, 0.1 mmo 1), KF (0.24 g.

4 mmo I), water (0.36 ml, 20 mmo
I), and 'BuOH (3 ml), and CO (50
a Lm) was sealed and reacted at 80°C for 48 hours. 3
Aqueous N-hydrochloric acid solution was added thereto, followed by extraction with ether, and the ether layer was washed with water and dried over 'Ag5Oa. After distilling off the ether under reduced pressure, the residue was recrystallized from ether-hexane to give 4.4.5.5-tetrafluoro-1,8=octanedioic acid in a yield of 0.24 g (97%). Obtained as a white powder.

mp　　　　　　　　204℃.

IR (KBr) 3450~3200am-' (Sh11
-M) 1710C11-' (c-o) River H-NMR (da-acetone, TMS) δ2.
1-3.0 (m, 8H).

"F-NMR (da-acetone, cPcls)
δ-115,9 (m, 4F).

Mass s/e(ral, int,)229(M
”-17,7), 208(10).

161 (10), 123 (37), 103 (1
00),? ? (40), 73 (40), 6G (5B)
, 55(7B), 47(47), 42(42).

28 (34).

Reference Example 8 1,6-diiodo of Reference Example 7 3. 3. 4. 4-
Tetrafluorohexane to 2,11-short-4,4
,5,5,6,6,7,7,8,8,9゜9-dodecafluorodecane (0.47 g, 1 mmol), 'B
The reaction was carried out under the same conditions as in Reference Example 7, except that the amount of uOH was changed to 5 ml. As a result, 2,11-dimethyl-4,4
,5,5,6,6,7,7,8°8,. 9.9-Dodecafluoro-1,12-dodecanedioic acid was obtained in a yield of 6794.

sp　　　149.5~151'e.

Anal, Ca1cd for CtJtaP
+tOe.

C: 35.46. H: 2.9B.

Found C: 35.56. H: 2.99°I
R (KBr) 3200~2800cm-'('a-N
) 1710 cm-'(νcoo) ・'H-NMR (d, -acstone+TMs) δ1.
33(d, J-8Hz, 6)1).

1.6 ~ 33-1 (+6H) + 11.0 (br, 2H)
.

”F-NMR (di-acetona, CFCIs)
δ-113,2 (br, 4F).

-121,6 (br, 4F), -123,7 (br, 4
F).

Mass s/e (tel, Int,) 457 (M”
-17,2), 430(14).

163 (21), 153 (22), 133 (33), 1
21 (32), 91 (60), 87 (30),
73 (75), 47 (10G), 45
(37).

41 (51), 2B (34).

Example 1 Example 2 4, 4. 5. 5. 6. 6. 7. 7. 8
．． 8. 9°9-Dodecafluoro-1,12-dodecanedioic acid (0,892 g, 2 mmol I) was heated to reflux in thionyl chloride (2 ml) under an Ar atmosphere for 2 hours.

As a result of distilling off excess thionyl chloride under reduced pressure, 4.4.
5,5.6.6,7,7,8,8,9.9-dodecafluoro-1,12-dodecanedioic acid chloride was obtained.

'H-NMR (CDCl2.TMS) 62.45 (
4H, tt, J-18 and 7Hz).

3.24 (4H, t, J-7Hz).

4, 4.5.5, 6, 6°7.7, obtained in Example 1
8.8.9.9-Dodecafluoro-1,12-dodecanedioic acid chloride was dissolved in toluene (2 tons) and then cooled with water. To this solution, add a toluene solution of HN (
1,3M, 3.1ml, 4mmol) and pyridine (
A mixed solution of 0.33ml (1°4 mmol) was slowly added and stirred for 15 minutes under water cooling. The generated pyridine hydrochloride was filtered and washed with toluene. Excess H from the filtrate
By removing N3 with an aspirator, 4
．． A toluene solution of 4,5,5,6,6.7.7.8.8°9.9-dodecafluoro-1,12-dodecanoic acid azide was obtained.

IR (KBr fixed cell, toluene
) 2145 cs-' (νN5) 1722es
-' (νCO), Example 3 4, 4, 5, 5, 6, 6° 7.7, obtained in Example 2
A toluene solution of 8,8.9.9-dodecafluoro-1,12-dodecanedioic acid azide was stirred at 95°C for 1 hour. As a result of distilling off the solvent under reduced pressure, 3, 3.4, 4, 5,
5,6,6,77.8.8-dodecafluoro-1,10
- diisocyanatodecane from Example 1 to 64% (0,
A total yield of 565 g).

Anal, Calcd for C+JsP+g
NmO wealth.

C: 32.74. H: 1.83. )h6.36
゜found C: 32.74. H: 1.8
3. N: 6.56゜IR (neat) 2270 cl
l-' (yNCO).

1190cs-' (C-F).

'H-NMR (CDC1x, TMS) δ2.40 (
48, tt, J-18 and 711z).

3.65(4)1. t, J-7Hz).

"F-11MR (COCl, CPCh) δ -114
,7(br,4F),-122,2(br,4F),-
124,1 (br, 4F).

Mass m/e (rel, lnt,) 4
40M”+1), 412,385 (3) 56 (100)
.

Example 4 4, 4. 5. 5. 6. 6. 7. 7-octafluoro-1,10-decanedioic acid (1,02 g, 2.
The 94th mm eye was treated with thionyl chloride (3 ml) under an Ar atmosphere.
) for 2 hours under reflux. Excess thionyl chloride was distilled off under reduced pressure, resulting in 4,4,5,5,6°6.7.
7-octafluoro-1,10-decanedioic acid chloride was obtained.

'H-NMR (CDC1s, TMS) δ2.53 (
411, tt, J-18 and 7Hz).

3.24 (4H, t, J-7Hz).

Summer R (KBr) 1795cm-' (ν co
).

Example 5 Chloride was dissolved in toluene (3 ml) and then cooled with water. To this solution, HN, toluene solution (1,3M
, 4.6m1.5.98mm and pyridine (0,4
A mixed solution of 9ml 1.6.05mmo I) was slowly added, and the mixture was stirred for 15 minutes under water cooling.

The resulting hydrochloride of gin was filtered and washed with toluene. By removing excess HN3 from the filtrate with an aspirator, 4,4,5,5°6.6.7.7-
A toluene solution of octafluoro-1,10-decanedioic acid azide was obtained.

IR (KBr fixed cell, toluene
) 2150 cm-' (νNs) 1722 cm-'
(νco).

Example 6 4, 4.5.5, 6.6°7°7- obtained in Example 4
Octafluoro-1,10-decanedioic acid CH*C
0N5 CO dew CHINCO obtained in Example 5, 4. 5. 5. 6. A toluene solution of 6°7.7-octafluoro-1,10-decanedioic acid azide was stirred at 95°C for 1 hour.

As a result of distilling off the solvent under reduced pressure, 3. 3. 4. 4゜5.5.6.6-octafluoro-1,8-diisocyanatooctane from Example 4 at 87% (0,867 g)
with an overall yield of .

IR(neat) 2280 am-' (vNco
).

1170 Yu-1 (C-V).

'II-NMR (CDCIslTMS) 62.41
(4H, tt, J-18 and 7H1).

3.66 (4H, t, J-7Hz).

"F-NMR (CDC1s, CFCls) δ-114,
9 (br, 4F), -124,1 (br, 4F).

Mass ale (rel, Int,) 341 (
284(2) Example 7 4.4.5.5-Tetrafluoro-1,8-octanedioic acid (0,537 g, 2.18 mmol) was mixed with thionyl chloride (2, 5ml) for 2 hours. Excess thionyl chloride was distilled off under reduced pressure.
．． 4,5.5-tetrafluoro-1,8-octanedioic acid chloride was obtained.

'II-NIIR (CDC1s4MS) 62.48
(4H, tt, J-18 and 711z).

3.22 (48,t, J-7Hz).

IR (lIBr) 1790m-Otori (ν..).

Example 6 CH Dew CH*C0C1 CH Snow CHICONs 4,4,5.5-tetrafluoro-1,8-octanedioic acid chloride obtained in Example 7 was dissolved in toluene (2.5 m
After dissolving in 1), the solution was cooled with water. Add H to this solution.
Ns toluene solution (1.3M3.4m 1.4.4
2 mmol) and pyridine (0.36 ml, 4.45
Slowly add the mixed solution of mmo I) and leave for 15 minutes under water cooling.
Stir for a minute. The generated pyridine hydrochloride was filtered and washed with toluene. Excess HN was removed from the filtrate using an aspirator to obtain a toluene solution of 4.4,5.5-tetrafluoro-1,8-octanioic acid azide.

IR(niBr fixed call, toluene
) 2130 css-' (Iis)1722cm-
'(1'-0).

Example 9 A toluene solution of 4,4.5.5-tetrafluoro-1,8-octanedioic acid azide obtained in Example 8 was heated at 95°C.
The mixture was stirred for 1 hour. As a result of distilling off the solvent under reduced pressure, 3.
3,4.4-tetrafluoro-1,6-dicyanatohexane was obtained from Example 7 in an overall yield of 78% (0,416 g).

IR (neat) 2275 cs-' (νo0).

1170 am-' (νc1).

'It-NM[1(CDC13,T?lS) δ2.
37(41(,tt,J-18and7)1z)3.
64 (48,t, J-7Hz).

"F-NMR (CDC1s, CFCl2) δ-115,
2 (br, 4F).

Mass s/e (ral, lnt,) 2
40M”+1), 184(16).

56 (100).

Example 10 IR (neat) 1790 cm-' (ν,.).

Example 11 ctt, CH32
, 11-dimethyl-4,4,5,5,6,6°7.7,
8.8.9.9-Dodecafluoro-112-dodecanedioic acid (0,192 g, 0.4 mmol) was heated to reflux in thionyl chloride (2 ml) under an Ar atmosphere for 1 hour.

As a result of distilling off excess thionyl chloride under reduced pressure, 2.11
-dimethyl-4,4゜5.5,6,6,7,7,8.8
, 9.9-dodecafluoro-1,12-dodecanedioic acid chloride was quantitatively obtained.

'H-NMR (CDCh, TMS) 61.49 (6
H, d, J-7, 211z), 2.17 (2H, m),
2.79 (2H, m), 3.32 (2H, ddq, J-
5,2゜7.2. and 7.2Hz).

2,11-dimethyl-4°4.5 obtained in Example 1O
,5,6.6,? , 7.8.8,9.9-dodecafluoro-1,12-dodecanedioic acid chloride was dissolved in toluene (2 m
After dissolving in 1), the solution was cooled with water. Add H to this solution.
A toluene solution of N s (1.3 M, 0.6 ml, 0.5
78mmo+) and pyridine (63μ1.0.78m
A mixed solution of mol) was slowly added thereto, and the mixture was stirred for 15 minutes under water cooling. The generated pyridine hydrochloride was filtered and washed with toluene. By removing excess HN from the filtrate with an aspirator, 2,11-dimethyl-4
, 4,5,5,6,6,7,7,8,8,99-dodecafluoro-1,12-dodecanedioic acid azide toluene solution was obtained.

IR(niBr fixed cell+toluene
) 2148 cs-'(s'Na) 1720cm
-' (PCO).

Example 12 6.6.7,7.8.8,9.9-dodecafluoro-2
, 11-diisocyanatododecane in Examples 1O to 9.
Obtained with an overall yield of 2% (0,172 g).

IR(neat) 2280 cm-'(1'NcO
).

1190 cm-' (C-F).

'H-IJ? 1R (CDCl2.TMS) 61.4
5<6H, d, J-7Hz), 2.3 (48a), 4.
12 (211,-).

"F-NMR (CDCJs, CFCIs) δ-114,
3 (4F, br), -122,1 (4F, br)
, -124,2 (4F, br).

Mass s/e (rel, int,) 469 (
M”+1), 468(M”).

390, 70 (100), 56 (1B), 42 (26)
.

C11s CHs 2,11-dimethyl-4°4.5,5 obtained in Example 11
．． 6.6.7.7.8,8.9.9 Dodecafluoro-1
, 12-dodecanoic acid azide was heated and stirred at 95° C. for 1 hour.

Claims (1)

[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, n is a natural number, X is -COY or -NCO, and Y is a halogen atom or N_3. ) A fluorine-containing α,ω-bifunctional compound represented by: