Reaction of 1,1,2-trifluoro-2-hexafluoro-2′-(heptafluoropropoxy)-propoxyethylene with amines or alcohols

Article abstract of DOI:10.1016/S0022-1139(00)00290-6

Reaction between 1,1,2-trifluoro-2-hexafluoro-2′-(heptafluoropropoxy)-propoxyethylene and secondary amines (dimethylamine, diethylamine, dibutylamine, pyrrolidine, piperidine, morpholine) leads either to perfluoro-2-propoxy-3(1H′)-ethoxy-2″-alkoxypropanes - the addition products to the double bond - or to an N,N-dialkylamide of α-substituted fluoroacetic acid depending on the solvent used and the following work-up of the crude product. With primary amines (propylamine, butylamine, monoethanolamine), fluorine-containing imines or N-alkylamides of the α-substituted fluoroacetic acid (as a mixture of diastereomers) were obtained. The use of diethanolamine produces 2-{fluoro-2[hexafluoro-2′-(heptafluoropropoxy)-propoxy]-methyl}-4,5,7,8- tetrahydro-[1.6.3]dioxasozine. Reaction of 1,1,2-trifluoro-2′-hexafluoro-2′-(heptafluoropropoxy)- propoxyethylene with alcohols (methanol, ethanol, β,β,β-trifluoroethanol, 2-methoxyethanol, 2-ethoxyethanol, iso-propanol, butanol and pentafluorophenol) in the presence of KOH in tetrahydrofuran (sulfolane, DMSO, acetonitrile) or sodium alkoxide in an alcoholic medium yields only the corresponding ethers as a mixture of diastereomers. Treatment of ethyleneglycol, glycerine, pentaerythritol, triethanolamine, 2-(2-hydroxyethylsulphanyl) ethanol, 4-(2-hydroxyethyl) phenol with 1,1,2-trifluoro-2′-(heptafluoropropoxy)-2-hexafluoropropoxyethylene provides the addition products to all OH groups if the reaction is carried out in DMSO, sulfolane or acetonitrile. However, the use of THF as the solvent leads to the formation of α-substituted tetrahydrofuran together with the formation of ethers. The initial perfluoro(propoxypropoxy) olefin can be hydrolyzed in the alkaline media to give fluoro-[hexafluoro-2-(heptafluoropropoxy)propoxy]acetic acid.

Full text of DOI:10.1016/S0022-1139(00)00290-6

Journal of Fluorine Chemistry 106 (2000) 13±24
Reaction of 1,1,2-tri¯uoro-2-hexa¯uoro-20-(hepta¯uoropropoxy)-
propoxyethylene with amines or alcohols
Georgii G. Furina,*, Luiza S. Pressmana, Leonid M. Pokrovskya,
Aleksei P. Krysina, Ki-Whan Chib
aInstitute of Organic Chemistry, Siberian Division of the Russian Academy of Sciences, 630090 Novosibirsk, Russia
bDepartment of Chemistry, University of Ulsan, Ulsan 680749, South Korea
Received 30 November 1999; accepted 15 March 2000
Abstract
Reaction between 1,1,2-tri¯uoro-2-hexa¯uoro-20-(hepta¯uoropropoxy)-propoxyethylene and secondary amines (dimethylamine,
diethylamine, dibutylamine, pyrrolidine, piperidine, morpholine) leads either to per¯uoro-2-propoxy-3(1H0)-ethoxy-200-alkoxypropanes
Ð the addition products to the double bond Ð or to an N,N-dialkylamide of a-substituted ¯uoroacetic acid depending on the solvent used
and the following work-up of the crude product. With primary amines (propylamine, butylamine, monoethanolamine), ¯uorine-containing
imines or N-alkylamides of the a-substituted ¯uoroacetic acid (as a mixture of diastereomers) were obtained. The use of diethanolamine
produces 2-{¯uoro-2[hexa¯uoro-20-(hepta¯uoropropoxy)-propoxy]-methyl}-4,5,7,8-tetrahydro-[1.6.3]dioxasozine. Reaction of 1,1,2-tri-
¯uoro-20-hexa¯uoro-20-(hepta¯uoropropoxy)-propoxyethylene with alcohols (methanol, ethanol, b,b,b-tri¯uoroethanol, 2-methoxyethanol,
2-ethoxyethanol, iso-propanol, butanol and penta¯uorophenol) in the presence of KOH in tetrahydrofuran (sulfolane, DMSO, acetonitrile)
or sodium alkoxide in an alcoholic medium yields only the corresponding ethers as a mixture of diastereomers. Treatment of
ethyleneglycol, glycerine, pentaerythritol, triethanolamine, 2-(2-hydroxyethylsulphanyl) ethanol, 4-(2-hydroxyethyl) phenol with 1,1,2-
tri¯uoro-20-(hepta¯uoropropoxy)-2-hexa¯uoropropoxyethylene provides the addition products to all OH groups if the reaction is carried out
in DMSO, sulfolane or acetonitrile. However, the use of THF as the solvent leads to the formation of a-substituted tetrahydrofuran together
with the formation of ethers. The initial per¯uoro(propoxypropoxy) ole®n can be hydrolyzed in the alkaline media to give ¯uoro-
[hexa¯uoro-2-(hepta¯uoropropoxy)propoxy]acetic acid. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: 1,1,2-Tri¯uoro-20-(hepta¯uoropropoxy)-2-hexa¯uoropropoxyethylene; Nucleophilic addition; Nucleophiles; Alcohols; Partially ¯uorinated
trialkylamines and dialkyl ethers
1. Introduction
nologies are known to give the desired products in low yields
due to the production of many by-products. For example,
¯uorination of trialkylamines by electrochemical ¯uorina-
tion in anhydrous hydrogen ¯uoride provided only 10±15%
yields of per¯uorinated products [8]. Fluorination of mono-
glyme and diglyme by F2 produced per¯uorinated products
with 21 and 16% yields, respectively [9±11]. Similar poor
results are obtained in the electrochemical ¯uorination with
these precursors [6]. The most successful result of direct
¯uorination was achieved by Lagow and co-workers [12,13].
Per¯uorination of partially ¯uorinated precursors obtained
by the reaction of nucleophilic reagents with per¯uoroole-
®ns [14] leads to better yields of per¯uorinated products
because of less decomposition. Thus, partially ¯uorinated
compounds have drawn much attention as precursors for the
synthesis of per¯uorinated materials [15±20]. This fact
triggered us to develop an ef®cient method for the synthesis
of partially ¯uorinated ethers and amino compounds.
Substitution of all the hydrogen atoms of trialkylamines
or dialkyl ethers by ¯uorine atoms leads to the formation of
per¯uorinated compounds with high thermal stability and
resistance towards oxidants. These compounds are also char-
acterized by low freezing points, high volatility, improved
electrophysical and lubricating properties [1]. They can be
used as effective liquid dielectrics, heat carriers, lubricants,
hydraulicliquids,cleanersofsiliconsemi-conductormatrixes,
and can also be applied in biology, medicine and chemical
vapor deposition of metal ®lms [2±5]. The substances of
these classes have been obtained, as a rule, either by
electrochemical ¯uorination [6], or by direct ¯uorination
of hydrocarbon precursors by F2 [7]. However, these tech-
* Corresponding author. Fax: ‡7-3832-344752.
E-mail address: furin@nioch.nsc.ru (G.G. Furin).
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 0 ) 0 0 2 9 0 - 6

14
G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
Scheme 1.
In the present paper, we would like to report a simple and
convenient method for the synthesis of partially ¯uorinated
trialkylamines and dialkyl ethers starting from commer-
cially available 1,1,2-tri¯uoro-(20-hepta¯uoropropoxy)-2-
hexa¯uoropropoxyethylene [21,22], which is obtained by
thermolysis of the per¯uoro-2(2-propoxy-20-propoxy) pro-
penyl ¯uoride in diglyme in the presence of Na2CO3
(Scheme 1) [23].
Scheme 3.
Formation of amides of acids has been observed earlier in
the reaction of hexa¯uoropropene with secondary amines in
an aqueous-ether medium [24].
Recently, authors of [25] have shown that the reaction of
secondary amines with compound 1 led to addition products
which were relatively stable at room temperature. These
adducts were easily transformed into the corresponding
amides of N,N-dialkyl-2H-per¯uoro-2(20-propoxypropoxy)
acetic acid by reaction with water [25].
2. Results and discussion
2.1. Reaction of 1,1,2-trifluoro-(20-heptafluoropropoxy)-2-
hexafluoropropoxyethylene with secondary amines
2.2. Reaction of 1,1,2-trifluoro-(20-heptafluoropropoxy)-2-
hexafluoro propoxyethylene with primary amines
Reaction of the alkene 1 with dimethylamine (or diethy-
lamine, dibutylamine, pyrrolidine, piperidine, morpholine)
in dry tetrahydrofuran leads to either addition products to the
double bond of 1, or N,N-dialkylamides of per¯uoro-20-
propoxy-200-propoxy¯uoroacetic acids depending on the
reaction conditions and the separation method of products.
Reaction of equimolar amounts of 1 with a secondary amine
yields mainly addition products to the double bond (2±7)
(Scheme 2). The ®nal products can be separated by direct
distillation of the reaction mixtures. The initial addition of
one equivalent of triethyl-amine followed by reaction with
water leads to N,N-dialkyl amides of per¯uoro-20-propoxy-
200-propoxyacetic acid (8±13) (Scheme 2).
Reaction of a primary amine (n-propylamine or n-butyl-
amine) with 1 in the presence of triethylamine followed by
an aqueous work-up provides the amide 16 or 17 (Scheme 3).
The ®rst step of that reaction might consist of the nucleo-
philic addition of a primary amine to the double bond of 1.
The product contains a CF2 group next to the NH fragment
and elimination of HF by Et3N forms a N=C bond. The
¯uorine atom at N=C bond is known to be reactive and
reaction with water transforms the imino group into the
corresponding amide. On the contrary, a fractional distilla-
tion immediately after the reaction of 1 with a primary amine
Scheme 2.

G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
15
2.3. Reaction of 1,1,2-trifluoro-(20-hepta-fluoropropoxy)-
2-hexafluoropropoxyethylene with alcohols in the presence
of base
Reaction between 1 and equimolar amounts of alcohol
(methanol, ethanol, 2,2,2-tri¯uoroethanol, 2-methoxyetha-
nol, 2-ethoxyethanol, propanol, butanol, 1-penta¯uorophe-
nyl-ethanol) or substituted phenols (penta¯uorophenol, 4-
(2-methoxyethyl) phenol) in THF (sulfolane, DMSO, acet-
onitrile) in the presence of an equimolar amount of KOH
leads to the addition products Ð per¯uoro-2-propoxy-
3(1,11)-ethoxy-200-alkoxypropanes Ð compounds (25±34)
(Scheme 6).
Scheme 4.
without any aqueous work-up gives the imine 14 or 15 even
in the absence of triethylamine. Treatment of 14 and 15 with
water provides 16 and 17, respectively. Reaction of 1 with
monoethanolamine occurs similarly to produce the corre-
sponding amide 18.
Quite unexpectedly reaction of 1 with diethanolamine in
the presence of Et3N in DMF leads to 19 instead of the
expected amide of ¯uoroacetic acid (Scheme 4).
Scheme 5 might be proposed as a plausible reaction
mechanism.
In the presence of Et3N, treatment of 1 with diethanola-
mine generates the intermediate 20. Elimination of ¯uoride
ion from 20 followed by an intramolecular nucleophilic
cyclization yields 22. The intermediate 22 can undergo a
ring expansion via intramolecular SN2 reaction to form the
bigger ring 19.
The same products can be obtained in better yields by the
treatment of 1 with sodium alkoxides in the corresponding
alcohols. The low yield with KOH in THF can be explained
by the fact that compounds 35 and 36 are formed from 1 in
the KOH±THF system (Scheme 7). A similar process was
observed in the reaction of per¯uoroalkoxy derivatives of
tri¯uoroethylene with THF in the presence of benzoyl
peroxide [26]. Therefore, THF or dioxane is not recom-
mended as a solvent in those reactions.
Reaction of 1 with other alcohols (ethylene glycol,
triethylene glycol, glycerine and pentaerythritol) also pro-
Scheme 5.
Scheme 6.

16
G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
Scheme 7.
vides addition products 40±43 (Scheme 8). DMSO, sulfo-
lane or MeCN can be used as solvents in this reaction.
A similar situation is observed in the reaction of com-
high reactivity towards nucleophilic reagents, which allows
us to develop a convenient method of the synthesis of
partially ¯uorinated amides of ¯uoroacetic acid, trialkyla-
mines and dialkyl ethers.
pound
1
with triethanolamine, 2-{(2-hydroxyethyl)-
(2,3,5,6-tetra¯uoro-4-tri¯uoromethylphenyl)-amine]-etha-
nol, 2-(2-hydroxyethylsulphanyl) ethanol and 4-(2-hydro-
xyethyl)-phenol. In these cases the polyethers 44±47 can be
obtained (Scheme 9).
Thus,
¯uoropropoxyethylene, a terminal per¯uoroole®n, shows
2.4. Spectroscopy
All the product structures were identi®ed by NMR, IR
and mass spectral data. The 1H NMR data of partially
¯uorinated trialkylamines, dialkyl ethers and amides of
1,1,2-tri¯uoro-20-(hepta¯uoropropoxy)-2-hexa-
Scheme 8.

G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
17
Scheme 9.
¯uoroacetic acid show the characteristic peaks of alkyl
groups (Table 1). The chemical shifts of 19F and spin±spin
coupling constants (JFF) for the group of C3F7OCF(CF3)C-
F2OCHF remain practically constant. An AB-system
(JFFˆ145±155 Hz) is observed in 19F NMR for the ¯uorine
atoms of CF2 groups in 5 and 8 positions. The main
differences are found in NMR spectra for CHF, C=O,
CHFCF2 groups (Tables 1 and 2).
The initial ole®n 1 contains an unsymmetrical carbon
atom (C4). Reaction of a nucleophile on the carbon atom of
the terminal double bond generates a second unsymmetrical
carbon atom (C6). That process produces a mixture of two
diastereomers (R,R±S,S and R,S±S,R), which are con®rmed
by the GC/MS and 19F NMR.
QF-1, Chromosorb W, column 4 m, diameter of 4 mm) with
detection katharometer by heat-conductivity, helium as the
carrier gas. The characteristics of products are given in
Tables 3 and 4.
3.2. Synthesis of olefin 1
To a suspension of Na2CO3 (54.0 g, 0.51 mol) in diglyme
(200 ml) at 208C was slowly added the ¯uoroanhydride of
¯uoride
per¯uoro-2-(2-propoxy-20-propoxy)-propenyl
(249 g, 0.5 mol) with a speed ensuring uniform evolution
of CO2 for 2 h. The resulting mixture was stirred at 208C for
4 h and left for 2 days. The mixture was distilled and a
fraction with bp 100±1058C was collected. The distillate was
washed with water and dried over MgSO4 to give the product
1 (151 g, 70%, bp 103±1048C). The 19F NMR spectrum (dF,
3. Experimental
CDCl3) of
3:2:3:2:1:1:2:1:1 at 83.8 (F7, CF3), 82.7 (F3, CF2), 82.3
(F8, CF3), 79.3 (F5, CF2), 48.9 (F2, CF, JF2,F1, 9, JF2,F1
1 contains nine signals with a ratio
3.1. Instrumentation
,
6 Hz), 41.3 (F1, CF, JF1, 6, JF1,F1, 11 Hz), 34.3 (F6, CF2),
28.2 (F1, CF, JF1,F2, 9, JF1,F1, 11 Hz), 19.3 (F4, CF). 13C
NMR (dF, CDCl3): 148.2 (C1, 1JCF 278.8; 2JCF 52.8), 130.5
The 1H and 19F NMR spectra were taken on a Bruker WP
200 SY spectrometer at 200.133, 188.291 MHz, and the 13
C
2
8
1
1
2
2
NMR spectra on a Bruker AM 400 spectrometer at
100.614 MHz. TMS and C6F6 were used as internal stan-
dards (JC±H was not determined). Infrared analysis was with
a FT/IR spectrometer Bruker IFS66 (5% in CCl4). High
resolution mass spectra were taken on a GC/MS spectro-
meter, Finnigan VG 707 OE and Hewlett Packard G 1800A
GCD with a HP-5 capillary column. All the reactions and
purity of individual sample were checked by 19F NMR
and GC. Reaction mixtures were analyzed by GC using a
LCM 72 chromatograph (Russia) (15% SE-30, SKTF-803:
(C , JCF 269.9; JCF 48.8), 118.6 (C , JCF 287.4; JCF
7
31.5), 118.1 (C , JCF 285.4; JCF 32.8), 117.4 (C , JCF
3
1
1
2
5
288.5; JCF 26.8), 116.5 (C , JCF 288.6; JCF 31.3), 107.6
2
1
2
6
(C , JCF 268.1; JCF 31.3), 103.7 (C , JCF 268.5; JCF
4
1
1
2
2
38.5). HRMS Calc. 431.9642 for C8F16O2 found 431.9640;
‡
mass spectrum, m/e (Irel, %): 432 [M] (6.22), 335
‡
‡
[M OCF=CF2]
‡
(6.57), 169 [C3F7]
(8.76), 119 [C2F5]
(68.42), 147
(13.48), 100
‡
[CF3CF=CF2]
‡
‡
‡
[CF2=CF2] (6.23), 97 [OCF=CF2] (4.17), 81 [CF=CF2]
‡
‡
(4.17), 69 [CF3] (100), 47 [COF] .

18
G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
Table 1
The 19F and 1H NMR spectra of new polyfluorinated compounds

G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
19
Table 1 (Continued )

20
G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
Table 2
The 13C NMR spectra of new polyfluorinated compounds

Table 2 (Continued )

22
G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
Table 3
Mass spectra data and physical characteristics of new compounds
Compound
Yield (%)
Bp (8C/Torr)
Found m/e
Formula
Calculated m/e
2
3
80
67
82
74
96
70
74
71
70
70
63
73
67
60
74
89
37±38/0.3
77±75/2
477.0218
505.0525
561.1173
503.0380
517.0531
519.0303
455.0200
483.0517
539.1139
481.0305
495.0500
497.0314
470.0259
484.0387
469.0345
483.0503
C
C
C
C
C
10H7F16NO2
12H11F16NO2
16H19F16NO2
12H9F16NO2
13H11F16NO2
477.0221
505.0534
561.1160
503.0377
517.0534
519.0326
455.0202
483.0515
539.1141
481.0358
495.0515
497.0307
470.0237
484.0393
469.0358
483.0515
4
77±78/0.3
56±57/0.5
61±62/0.3
82±83/0.2
57±58/0.2
77±78/2
5
6
7
C12H9F16NO3
8
C
C
10H7F14NO2
12H11F14NO3
9
10
11
12
13
14
15a
16
17
110±112/2
92±93/0.4
140±141/0.5
143±144/0.5
89±90/0.4
41±43/0.2
77±78/0.4
85±86/0.4
C16H19F14NO3
C
C
C
12H9F14NO3
13H11F14NO3
12H9F14NO4
C11H8F15NO2
C12H9F15NO2
C
C
11H9F14NO3
12H11F14NO3
‡
a [M H] .
3.3. Reactions of 1 with amines
mixture was poured into water and the organic layer was
separated. The organic phase was dried over MgSO4 and
distilled to provide N,N-dibutyl±2H-per¯uoro-2(20-propox-
ypropoxy) acetic amide (17) (4.6 g, 95.2%). IR: 2984, 2956,
2940 (C±H), 1674 (C=O), 1452, 1332 (C±N), 1252±1160
(a) To a solution of 1 (17.28 g, 40 mmol) in THF (10 ml),
was added a solution of pyrrolidine (2.84 g, 40 mmol) in
THF (10 ml) for 0.5 h at 08C. The mixture was stirred at 08C
for 1 h, then at 208C for 6 h. The solvent was evaporated in
vacuum and the rest was distilled to yield 1-[2H-per¯uoro-
2(propoxy)-propoxy)ethyl]pyrrolidine (5) (15.0 g, 74.5%,
bp 56±578C/0.5 Torr).
1
(C±F) cm (see [27]).
(e) To a solution of 1 (8.6 g, 20 mmol) in THF (10 ml),
was added a solution of n-propylamine (1.18 g, 20 mmol)
and triethylamine (2.02 g, 20 mmol) in THF (15 ml) for
15 min at 08C. The reaction mixture was stirred at 208C for
10 h. The resulting solution was poured into water and the
organic layer was separated. The organic phase was dried
over MgSO4 and distilled to produce N,N-dipropyl-2H-per-
¯uoro-2(20-propoxypropoxy) acetic amide (16) (8.4 g,
90%).
(f) To a solution of 1 (2.2 g, 50 mmol) in DMF (25 ml),
was added a mixture of monoethanolamine (3.0 g, 50 mmol)
and triethylamine (10.1 g, 50 mmol) for 0.5 h at 08C. The
resulting solution was stirred at 208C for 4 h. The reaction
mixture was poured into 10% aqueous HCl (50 ml). The
crude products were extracted with CH2Cl2 and dried over
CaCl2. Distillation of the crude products provided the 2-
¯uoro-2{hexa¯uoro-20-(hepta¯uoropropoxy)propoxy]-N(2-
hydroxyethyl) acetic amide (18) (16.8 g, 70%, bp 56±578C/
0.2 Torr). Calc. C 25.48; H 1.49; F 56.48; N 2.97
C10H7F14NO4 found C 25.33; 25.16; H 1.35; 1.41; F
56.70; 56.54; N 3.16.
Reactions of compound 1 with other amines were carried
out by similar procedures (Tables 1±3).
(b) To a solution of 1 (15.12 g, 35 mmol) in THF (10 ml),
was added a solution of diethylamine (2.56 g, 35 mmol) and
triethylamine (3.54 g, 35 mmol) in THF (10 ml) for 0.5 h at
08C. The mixture was stirred at 08C for 1 h, then at 208C for
6 h. The resulting solution was poured into water and the
organic phase was separated. The organic phase was washed
with water and dried over MgSO4. Distillation of the crude
product provided N,N-diethylamino-2H-per¯uoro-2(2-pro-
poxypropoxy) acetamide (9) (12.0 g, 71%, bp 77±788C/
2 Torr).
(c) To a solution of 1 (12.0 g, 28 mmol) in THF (10 ml),
was added a solution of n-butylamine (4.02 g, 55 mmol) in
THF (10 ml) for 0.5 h at 08C. The mixture was stirred at
208C overnight. The resulting solution was ®ltered and the
®ltrate was distilled to give (8.06 g, 60%, bp 41±438C/
0.2 Torr) of 1,2-di¯uoro-2[20(hepta¯uoropropoxy)-hexa-
¯uoropropoxy)-ethylidene] propylamine (15) (8.06 g,
60%, bp 41±438C/0.2 Torr). IR: 2960, 2892, 2876 (C±H),
(g) A solution of 1 (24.0 g, 56 mmol), diethanolamine
(5.9 g, 56 mmol) and triethylamine (10.1 g, 56 mmol) in
DMF (25 ml) was stirred at 1008C for 4 h. The reaction
mixture was poured into water and the organic layer was
separated. The organic phase was dried over CaCl2 and
distilled to produce 2-{2-¯uoro-2[hexa¯uoro-20-(hepta-
¯uoropropoxy)propoxy]-methyl}-4,5,7,8-tetrahydro-[1.6.3]-
dioxasozine (19) (25.0 g, 87.4%, bp 79±808C/0.4 Torr). IR:
1
1720, 1536 (C=N), 1332 (C±N), 1252±1160 (C±F) cm
(see [27]).
Product 14 was obtained by a similar procedure (Tables 1±
3).
(d) A solution of 15 (4.84 g, 10 mmol) in THF (30 ml) and
water (10 ml) was stirred at 208C for 5 h. The reaction

G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
23
Table 4
Physical constants and analytical data of new polyfluorinated ethers
Compound
Yield (%)
Bp (8C/Torr)
Found (%)
C
Formula
Calculated (%)
H
F
C
H
F
25
26
27
28
29
30
31
32
33
34
35
37
38
39
40
41
42
43
44
45
46
47
35
54a
130
23.27
23.48
25.82
25.51
27.18
27.34
27.07
26.93
28.38
28.67
26.27
26.48
28.10
28.30
30.05
30.03
22.46
22.54
29.52
29.53
28.56
28.73
26.88
26.87
35.65
35.41
34.75
34.95
23.83
23.52
26.16
26.38
23.17
22.88
23.89
24.03
25.26
25.80
24.74
24.65
28.03
27.89
29.27
29.15
0.86
0.90
1.26
1.13
1.43
1.46
1.70
1.62
1.97
1.87
1.65
1.80
1.92
2.13
0.70
0.72
0.55
0.52
0.77
0.92
1.63
1.54
0.20
0.07
2.03
2.15
1.79
1.50
0.59
0.88
1.25
1.55
0.49
0.34
0.68
0.90
1.11
1.25
0.97
1.14
1.20
0.99
1.05
1.27
65.52
66.48
64.03
64.08
61.00
61.16
61.75
62.00
61.17
61.57
59.05
58.87
58.91
59.07
61.84
61.67
68.27
68.61
60.46
60.64
60.97
61.11
65.75
65.85
52.04
51.76
48.89
48.96
66.82
66.57
59.80
59.87
66.02
65.93
64.85
64.96
62.83
62.99
61.26
61.58
62.68
62.84
61.61
61.50
C9H4F16O3
23.29
0.87
65.50
63.58
73
60/24
C10H6F16O3
25.12
26.85
1.26
1.64
58a
50
28/20
52a
C11H8F16O3
61.76
76
66±67/7
180
25
33a
C
12H10F16O3
11H8F16O4
28.46
25.98
27.60
29.81
22.56
29.09
28.57
27.27
34.93
34.73
23.33
26.04
23.34
23.82
1.99
1.59
1.93
0.78
0.57
0.76
1.59
0.16
2.05
1.96
0.65
1.38
0.58
0.64
1.04
1.01
0.84
1.00
60.07
59.84
58.21
61.96
67.85
60.45
60.32
64.77
52.05
48.97
65.66
59.96
65.71
65.24
63.11
61.66
62.53
60.68
80
80/10
C
79a
48
80/6
C12H10F16O4
34a
74
131/13
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
16H5F21O3
10H3F19O3
16H5F21O4
12H8F16O3
14HF21O3
71
71a
137±140
110/0.4
63±64/0.3
68/0.15
105/0.05
138/0.11
143/10
67
80
74
78
64
50
76
82
95
80
81.5
90
77
17H12F16O4
18H12F16O5
18H6F32O6
22H14F32O8
27H8F48O9
37H12F64O12
137±139/0.3
126±127/0.8
179±180/0.15
175/0.04
145/0.3
163±164/0.05
160/0.08
30H15F48NO9 24.91
20H10F32O6S 24.34
27H10F39NO6 27.34
24H10F32O6
28.74
a Reaction of alcohol in the presence of Et3N in THF.
2920 (C±H), 2890, 1460 (C=N), 1320 (C±N), 1300 (C±O),
1
and 79.0 (AB-system JFF 160 Hz, F5, CF2), 23.7 (F6, CF, JFH
‡
56 Hz), 83.9 (F12, CF3). GC/MS, m/e (Irel, %): 478 [M F]
1150±1250 (C±F), 1020 (C±O), 990 cm
1
.
1H NMR
(CDCl3): 5.80 (H6, H, JHF 56 Hz), 3.97 (H9, 2H), 3.88
(H10, 2H), 3.25 (H8, 2H), 2.98 (H11, 2H). 13C NMR (CDCl3)
(7.47), 467 [M CH2O] (15.27), 335 [M HOCH2CH2-
‡
‡ ‡
C=NCH2CH2OH] (4.68), 312 [M C3F7O] (0.77), 169
1
2
1
‡ ‡
1
2
dC, JCF: 117.1 (C , JCF 286.6; JCF 33), 106.6 (C , JCF
268.3; JCF 37.5), 116.2 (C , JCF 288.6; JCF 30.6), 103.1
[C3F7] (18.34), 162 [M C3F7OCF(CF3)CF2] (0.52), 146
‡
3
‡
2
1
2
[M C3F7OCF(CF3)CF2O] (21.60), 119 [C2F5] (3.55),
‡
4
(C , JCF 276.8; JCF 37.7), 115.3 (C , JCF 268.2; JCF
5
1
2
1
2
116 [OCFCF3] (1.20), 114 [M H2O, C3F7OCF(CF3)CF2-
‡
6
28.8), 102.4 (C , JCF 230.9; JCF 45.5), 119.3 (C , JCF
7
2
‡
‡
1
2
OCHF] (100), 100 [CF2=CF2] (2.14), 72 [CHFC=NCH2]
8
9
12
‡
‡
1
2
24.8), 65.5 (C ), 52.6 (C ), 118.4 (C , JCF 287.2; JCF
31.2), 64.8 (C11), 52.5 (C10). 19F NMR (CDCl3), dF: 82.4
(F1, CF3), 34.3 (F2, CF2), 82.9 (F3, CF2), 19.4 (F4, CF), 81.3
(6.46), 69 [CF3] (18.23), 44 [CH2CH2O] . Calc. (%) C
28.97; H 1.81; F 53.52; N 2.82 C12H9F14NO4 found C 28.67,
28.89; H 1.69, 1.83; F 53.23, 53.45; N 2.68.

24
G.G. Furin et al. / Journal of Fluorine Chemistry 106 (2000) 13±24
‡
‡
(h) To a solution of 1 (17.28 g, 40 mmol) in THF (50 ml),
%): 383 [M COOH] (20.62), 335 [M COOH, OCHF]
(30.36), 169 [C3F7] (100), 150 [C3F6] (17.39), 119
‡ ‡
was added 1 M solution (40 ml) of sodium methoxide in
methanol for 0.5 h at 08C. The resulting solution was stirred
at 208C overnight. The reaction mixture was poured into
water and the organic layer was separated. The organic
phase was dried over MgSO4 and distilled to give 2-meth-
oxy-1H-per¯uoro-(ethoxy)-2-propoxypropane (25) (10.0 g,
54%). IR: 1160±1260 (C±F), 1300 (C±O), 290, 2980 (C±H)
‡
‡
[C2F5]
[CHFCOOH] (91.84), 69 [CF3] (76.14), 49 [FCH2O]
(19.90), 100 [CF2=CF2]
‡
(16.10), 77
‡
‡
‡
‡
(29.21), 45 [COOH] (6.89), 29 [CHO] (13.74).
Acknowledgements
‡
cm 1 ([27]). GC/MS, m/e (Irel, %): 445 [M H] (1.51), 395
‡
‡
‡
[M CF3] (0.65), 169 [C3F7] (31.69), 119 [C2F5] (5.84),
‡
The authors are grateful to the KISTEP in Korea and
Innovation grant RAS DS, N 2 (1998±99) (Russia) for their
®nancial supports for this work.
‡
113 [CH3OCF2CHF] (67.24), 100 [CF2=CF2] (5.74), 81
‡
‡
‡
[CF2OCH3] (100), 69 [CF3] (30.30), 63 [CH3OCHF]
‡
(46.49), 31 [OCH3] (2.54).
Reaction of 1 with other alcohols in the presence of KOH
in an appropriate alcohol were carried out by similar pro-
cedures (Tables 1, 2 and 4).
References
(i) To a suspension of KOH (3.4 g, 60 mmol) in THF
(50 ml), was added a mixture of 2-ethoxyethanol (3.6 g,
40 mmol) and 1 (17.28 g, 40 mmol) at 508C. The reaction
mixture was stirred at 508C for 18 h and poured into water.
The organic layer was separated and dried over MgSO4. The
crude products were distilled to produce 1-{2[2-(2-ethoxy-
ethoxy)-1,2,2-tri¯uoroethoxy]-1,2,2-tri¯uoro-1-tri¯uoro-
methyl-ethoxy}-hepta¯uoropropane (33) (10.0 g, 48%).
HRMS Calc. 521.0105 for C13H9F12O8 found 521.0105.
[1] N. Ishikawa (Ed.), Novoe v technologii soedinenii ftora, Per. Iz
Japaneze, Moskow, Mir, 1984, p. 591.
[2] W.R. Jones, T.R. Bierschenk, T.J. Juhlke, H. Kawa, R.J. Lagow, J.
Ind. Eng. Chem. Res. 27 (1988) 1497.
[3] J. Brodbelt, S. Maleknia, C.-C. Liou, R.J. Lagow, J. Am. Chem. Soc.
113 (1991) 5913.
[4] K.-G. Sung, R.J. Lagow, J. Am. Chem. Soc. 117 (1995) 4276.
[5] T. Furuya, K. Kono, S. Sasamoto, I. Myata, Jpn. Kokai Tokkyo Koho
PJ 08 259482 (1996) (Hitachi Maxell, Japan); Chem. Abstr. 126
(1997) 31072z.
‡
GC/MS, m/e (Irel, %): 521 [M H] (0.06), 473 [M C2H5,
‡
[6] G.G. Furin, P.G. Gambaretto, Fluorination of Organic Compounds,
CLEUP, Padua, Italy, 1996, p. 212.
‡
‡
HF] (0.13), 169 [C3F7] (21.81), 150 [C3F6] (3.80), 119
‡
‡
[7] R.J. Lagow, T.R. Bierschenk, T.J. Juhlke, H. Kawa, in: G.A. Olah,
R.D. Chambers, G.K. Surya Prakash (Eds.), Synthetic Fluorine
Chemistry, Wiley, 1992, pp. 97±126.
[C2F5] (97.14), 100 [CF2=CF2] (5.57), 73 [CH2CH2-
‡
‡
‡
OC2H5] (11.08), 69 [CF3] (31.25), 59 [CH2OC2H5]
‡
‡
(99.99), 45 [OC2H5] (87.48), 31 [OCH3] (36.88).
Reactions of 1 with other alcohols were carried out by
similar procedures (Tables 1, 2 and 4).
[8] G.G. Furin, Sov. Sci. Rev. B. Chem. 16 (1991) 1.
[9] T.R. Bierschenk, T.J. Juhlke, H. Kawa, R.J. Lagow, US Patent
5093432 (1992); 5461117 (1995); 5523496 (1996) (Exfluor Research
Corp); Russ. Chem. Abstr. (1998) 8H95.
(j) A mixture of 1 (43.2 g, 100 mmol) and KOH (5.6 g,
100 mmol) in THF (50 ml) was stirred at 808C for 24 h. The
reaction mixture was poured into water and extracted with
diethyl ether. The organic phase was dried over MgSO4 and
distilled to provide 2{1,1,2-tri¯uoro-2[hexa¯uoro-2(hepta-
¯uoropropoxy)propoxy]ethyl}tetrahydrofuran (35) (40.3 g,
80%, bp 63±648C/0.3 Torr). IR: 2900 (C±H), 2300, 1325
[10] J.L. Adcock, R.J. Lagow, J. Org. Chem. 38 (1973) 2617.
[11] J.L. Adcock, R.A. Beh, R.J. Lagow, J. Org. Chem. 40 (1975) 3271.
[12] R.J. Lagow, US Patent 4788350 (1988); Chem. Abstr. 110 (1989)
212130.
[13] W.-H. Lin, W.D. Clark, R.J. Lagow, J. Org. Chem. 54 (1989) 1990.
[14] V.F. Snegirev, E.V. Zhacharova, K.N. Makarov, I.L. Knunyanz, Izv.
Akad. Nauk USSR, Ser. Khim. (1983) 2561.
[15] T. Ono, K. Yamanouchi, K.V. Scherer, J. Fluorine Chem. 73 (1995)
267.
(C±O), 1300 (C±O), 1150±1250 (C±F), 990 (C±O),
1
965 cm
C12H7F16O3 found [M H] 503.0136. GC/MS m/e (Irel,
(see [27]). HRMS Calc. 503.0139 for
‡
[16] A.A. Kadyrov, L.L. Gervits, L.F. Komarova, K.N. Makarov, J.
Fluorine Chem. 45 (1989) 152.
‡
‡
[17] D.D. Moldavsky, G.I. Kaurova, T.A. Bispen, G.G. Furin, J. Fluorine
Chem. 63 (1993) 193.
%): 503 [M H] (0.47), 383 [M H C2F5] (20.62), 335
‡
[M OCHFCF2CHCH2CH2CH2O] (30.36), 169 [OCHF-
‡
[18] D.D. Moldavsky, G.G. Furin, Zh. Prikl. Khim. 65 (1995) 1721.
[19] A. Feiring, E.E.R. Wonchoda, J. Org. Chem. 70 (1992) 1014.
[20] C.G. Krespan, F.A. Van-Catledge, B.E. Smart, J. Am. Chem. Soc.
106 (1984) 5544.
‡
CF2CHCH2CH2CH2O]
(100), 167 [OCF(CF3)CF2]
‡
‡
(3.58), 150 [CF2CFCF3] (17.39), 119 [C2F5] (19.90),
‡
‡
‡
100 [CF2=CF2]
(20.11), 69 [CF3] (76.14).
(16.10), 71 [CH2CH2CH2CH2O]
[21] K.-W. Chi, G.G. Furin, Bull. Korean Chem. Soc. 20 (1999) 495.
[22] K.-W. Chi, G.G. Furin, Bull. Korean Chem. Soc. 20 (1999) 220.
[23] V.S. Yuminov, Zh. Obshch. Khim. 31 (1995) 1142.
[24] M. Kuroboschi, T. Ishihara, Bull. Chem. Soc. Jpn. 64 (1990) 1191.
[25] I. Dlouha, O. Poleta, in: 12th European Symposium on Fluorine
Chemistry, Berlin, Germany, 29 August±2 September, 1998,
Abstracts, p. 60.
The aqueous phase was neutralized with 10% aqueous
HCl and extracted with diethyl ether. The extract was dried
over MgSO4 and distilled to provide ¯uoro-[hexa¯uoro-2-
(hepta¯uoropropoxy)propoxy] acetic acid (36) (8.56 g,
20%, bp 71±728C/0.3 Torr). IR: 3000, 2500, 2900 (C±H),
1760 (C=O), 1450 (C±N), 1310, 1325 (C±O), 1160±1200
[26] J.-G. Chen, Y.-F. Zhang, X.-M. Aheng, D. Vij, K. White, R.L.
Kirchmeier, J.M. Shreeve, Inorg. Chem. 35 (1996) 1590.
[27] L. Bellami, Infra-Red Spectra of Complex Molecules, Wiley, New
York, 1954, p. 590.
1
(C±F), 980 cm (see [26]). HRMS Calc. 382.9753 for
‡
C7HF14O2 [M COOH] found 382.9750. GC/MS, m/e (Irel,