Electrochemical fluorination of (N,N-dialkylamino)alcohols

Article abstract of DOI:10.1016/S0022-1139(99)00053-6

Series of amino alcohols including 2-(N,N-dialkylamino)ethanols, 3-(N,N-dimethylamino)propanol and 4-(N,N-dimethylamino)butanol were subjected to electrochemical fluorination. In the case of 2-(N,N-dialkylamino)ethanols, the F-(2-N,N-dialkylamino)acetyl fluorides were obtained in fair to good yields. Yields of each target compound were strongly dependent on the kind of the dialkylamino group. Cyclic amines having an N-(2-hydroxylethyl) group afforded the corresponding F-[N-(c-alkylamino)-substituted acetyl fluorides]. Their yields were generally better than those of acyclic analogs. Several 2-(N,N-dialkylamino)ethanols and 3-(N,N-dimethylamino)propanol were converted into the corresponding trimethylsilylethers, aminoalkyl methyl carbonates and bis-aminoalkyl carbonate, respectively, and they were subjected to fluorination for a comparison of the yield with that obtained from that of the parent aminoalcohol.

Full text of DOI:10.1016/S0022-1139(99)00053-6

Journal of Fluorine Chemistry 97 (1999) 229±237
Electrochemical ¯uorination of (N,N-dialkylamino)alcohols
Takashi Abea,*, Haruhiko Fukayaa, Eiji Hayashia, Taizo Onoa, Masakazu Nishidaa,
Irina Soloshonoka, Kunio Okuharab
aNational Industrial Research Institute of Nagoya Hirate-cho 1-1, Kita-ku, Nagoya 462-8510, Japan
bDepartment for the New Refrigerant and Other Substances Research, Research Institute of Innovative Technology for the Earth,
Hongo Wakai Bidg. 6F, 2-40-17, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Received 30 November 1998; received in revised form 6 January 1999; accepted 7 January 1999
Dedicated to Prof. Y. Kobayashi on the occasion of his 75th birthday
Abstract
Series of amino alcohols including 2-(N,N-dialkylamino)ethanols, 3-(N,N-dimethylamino)propanol and 4-(N,N-dimethylamino)butanol
were subjected to electrochemical ¯uorination. In the case of 2-(N,N-dialkylamino)ethanols, the F-(2-N,N-dialkylamino)acetyl ¯uorides
were obtained in fair to good yields. Yields of each target compound were strongly dependent on the kind of the dialkylamino group. Cyclic
amines having an N-(2-hydroxylethyl) group afforded the corresponding F-[N-(c-alkylamino)-substituted acetyl ¯uorides]. Their yields
were generally better than those of acyclic analogs. Several 2-(N,N-dialkylamino)ethanols and 3-(N,N-dimethylamino)propanol were
converted into the corresponding trimethylsilylethers, aminoalkyl methyl carbonates and bis-aminoalkyl carbonate, respectively, and they
were subjected to ¯uorination for a comparison of the yield with that obtained from that of the parent aminoalcohol. # 1999 Elsevier
Science S.A. All rights reserved.
Keywords: Electrochemical ¯uorination; Per¯uoroacid ¯uorides; Ethanolamines; Propanolamines; Trimethylsilyl ethers; Carbonates
1. Introduction
cyclic N,N-dialkylamino-substituted alcohols as the starting
materials for preparing nitrogen-containing F-carboxylic
acid ¯uorides. We now present the results of the electro-
chemical ¯uorination of the following eight N,N-dialkyla-
mino-substituted alcohols 1ꢀ4, 10ꢀ13 including their
trimethylsilyl derivatives of 5, 8, 14 and 15, aminoalkyl
methyl carbonates 6 and 9 and bis-2-(N,N-dimethylami-
no)ethyl carbonate (7): (CH3)2NCH2CH2OH (1), (CH3)2-
NCH2CH2CH2OH (2), (CH3)2NCH2CH2CH2CH2OH (3),
(C2H5)2NCH2CH2OH (4), (CH3)2NCH2CH2OSi(CH3)3
(5), (CH3)2NCH2CH2OC(O)OCH3 (6), [(CH3)2NCH2-
CH2O]2C=O (7), (CH3)2NCH2CH2CH2OSi(CH3)3 (8),
(CH3)2NCH2CH2CH2OC(O)OCH3 (9), c-(CH2)4NCH2-
CH2OH (10), c-O(C2H4)2NCH2CH2OH (11), c-(CH2)5-
NCH2CH2OH (12), c-HN(CH2)4NCH2CH2OH (13), c-
(CH2)4NCH2CH2OSi(CH3)3 (14), c-O(C2H4)2NCH2CH2O-
Si(CH3)3 (15).
F-carboxylic acids are very important as versatile starting
materials for the synthesis of organo¯uorine chemicals [1,2].
Although many approaches have been developed for pre-
paring F-carboxylic acids, there is still a need to develop
more ef®cient and practical methodology. Presently, various
kinds of F-(N,N-dialkylamino)acetyl ¯uorides and F-(N,N-
dialkylamino)propionyl ¯uorides have been prepared by the
¯uorination of methyl esters of N,N-dialkylamino-substi-
tuted acetic acids [3±7], and methyl esters [3±7] or acid
chlorides [8] of N,N-dialkylamino-substituted propionic
acids. While it has been reported that electrochemical
¯uorination of alcohols having a short alkyl chain gave
the corresponding F-carboxylic acid ¯uorides in good yields
[9±11], there have been no reports dealing with the ¯uor-
ination of 2-(N,N-dialkylamino)ethanol1. Thus, it seemed to
be of interest to investigate the ¯uorination of acyclic and
2. Results and discussion
*Corresponding author. Tel.: +81-52-911-2111; fax: +81-52-916-2802;
e-mail: abe@nirin.go.jp
1Several diethanolamines have been subjected to electrochemical
fluorination; see [12].
It is known that oxygen-containing compounds which
have two to four carbon atoms, such as alcohols, esters and
0022-1139/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 0 5 3 - 6

230
T. Abe et al. / Journal of Fluorine Chemistry 97 (1999) 229±237
(N,N-dimethylamino)ethanol (1), 3-(N,N-dimethylamino)-
propanol (2), and 4-(N,N-dimethylamino)butanol (3) was
investigated (Runs 1ꢀ3 in Table 1). It was found that the
expected N-containing F-carboxylic acid ¯uorides such as
F-N,N-dimethylaminoacetyl ¯uoride (19) (yieldˆ12.5%),
F-2-(N,N-dimethylamino)propionyl ¯uoride (20) (yieldˆ
5.3%), and F-3-(N,N-dimethylamino)butyryl ¯uoride (21)
(yieldˆ1.2%) were formed from these aminoalcohols 1ꢀ3.
However, their yields decreased in the order of the ¯uor-
ination of 1±3. For example, as a typical case of the ECF of
these alcohols, from 1, the following various ¯uorinated
products were obtained along with the expected 19 (Scheme
3).
Scheme 1.
Scheme 2.
As a result of reaction of the hydroxyl group of 1, not only
F-N,N-dimethylethylamine (24) but also F-bis-2-(N,N-
dimethylamino)ethyl ether (25) were obtained as the ®nal
¯uorination products. Apparently, compound 25 was
formed due to the intermolecular dimerization of 1. Simi-
larly, in the ¯uorination of 2, F-bis-3-(N,N-dimethylami-
no)propyl ether (26) (yieldˆ1.3%) and its degraded
products, such as F-3-(N,N-dimethylamino)propyl F-ethyl
ether (27) and F-3-(N,N-dimethylamino)propyl F-propyl
ether (28), were formed as the ¯uorination products which
were derived from the condensation of 2.
aldehydes, can be used as starting materials for the pre-
paration of F-carboxylic acid ¯uorides by electrochemical
¯uorination [9±11]. The formation of F-acid ¯uorides (16)
from alcohols is explained by successive ¯uorination invol-
ving an initial substitution of the hydrogen ꢀ to the hydroxyl
group of alcohols by ¯uorine followed by the subsequent
elimination of HF to form an aldehyde (17) or an acid
¯uoride (18) (Scheme 1).
Although most hydroxyl groups of primary alcohols exist
as oxonium ions in anhydrous hydrogen ¯uoride (AHF), the
elimination of the hydroxyl group to form a carbonium ion
is a major side reaction that results in lowering the yield of
the desired F-acid ¯uorides (Scheme 2).
In the case of ¯uorination of 3, the product distribution
pattern was different from that of 1 or 2. A large quantity of
F-n-butyryl ¯uoride (29) was formed as a result of the
cleavage of the C±N bond of 3 (Scheme 4).
In the case of aminoalcohols, which contain both nitrogen
and oxygen atoms in the molecule, one can assume that their
behavior in AHF would be more complex than that of
alcohols [13]. In order to examine the ¯uorination of
aminoalcohols represented as R2N±(CH2)n±OH where
nˆ2, 3, 4, the electrochemical ¯uorination (ECF) of 2-
From the ECF of 2-(N,N-diethylamino)ethanol (4), F-N-
ethylmorpholine (31) was obtained as the cyclization pro-
duct along with the desired F-(N,N-diethylamino)acetyl
¯uoride (32) (Scheme 5).
Compound 31 was formed as a result of the cyclization of
4 during ECF. Similarly, it has been reported that compound
Scheme 3.
Scheme 4.

Table 1
Results of the fluorination of 1±9
Run
Sample g(mol)
Current passed
(Ahr)
Fluorinated
product (g)
Acid fluoride (yield %)
Othersc (yield %)
1
(CH3)2NCH2CH2OH (1) 39.5 (0.443)
274
27.9a (1.9)b
ꢁCF3†2NCF2 C F (19) (12.5)
(CF3)3N (22) (3.6), (CF3)2NCHF2 (23) (2.2),
(CF3)2NC2F5 (24) (1.6),
k
O
(CF3)2NCF2CF2OCF2CF2N(CF3)2 (25) (0.8)
22 (2.2), 23 (3.2), 24 (3.0), C2F5N(CHF2)CF3
(42) (1.1) C3F7N(CF3)2 (35) (1.3), C3F7N(CHF2)CF3
(36) (0.9), (CF3)2NCF2CF2CF2OC2F5 (27) (0.2),
(CF3)2NCF2CF2CF2OC3F7 (28) (6.7),
2
(CH3)2NCH2CH2CH2OH (2) 39.9 (0.386)
251
23.1 (4.8)
ꢁCF3†2NCF2CF2 C F (20) (5.3)
k
O
(CF3)2NCF2CF2CF2OCF2CF2CF2N(CF3)2 (26) (1.2)
C2F5 C F (8.9), C3F7 C F (29) (17.2), 35 (2.0)
3
4
(CH3)2NCH2CH2CH2CH2OH (3) 39.6 (0.338)
(C2H5)2NCH2CH2OH (4) 40.3 (0.344)
275
275
19.8 (25.4)
19.8 (25.4)
ꢁCF3†2NCF2CF2CF2 C F (21) (1.2)
k
k
k
O
O
O
C4F9N(CF3)2 (30) (0.5)
(C2F5)2NCF3 (33) (4.5), (C3F5)3N (34) (6.3),
ꢁC2F5†2NCF2 C F (32) (9.0)
k
O
5
6
(CH3)2NCH2CH2OSi(CH3)3 (5) 31.6 (0.196)
ꢁCH3†2NCH2CH2O C OCH3 (6) 30.2 (0.206)
172
176
19.8a (0)b
8.6 (0)
19 (8.1)
19 (7.3)
24 (1.2)
22 (1.9), 23 (0.8), 24 (3.4)
k
O
7
8
9
|(CH3)2NCH2CH2O|2C=O (7) (26.0) (0.148)
(CH3)2NCH2CH2CH2OSi(CH3)3 (8) 35.0 (0.200)
ꢁCH3†2NCH2CH2CH2O C OCH3 (9) 30.1
176
213
179
13.4 (0)
22.1 (3.7)
9.8 (0)
19 (12.8)
20 (6.1)
20 (4.5)
22 (3.3), 23 (2.1), 24 (12.2)
24 (3.0), 35 (1.8), 27 (0.8), 28 (1.7), 26 (1.0)
22 (1.4), 23 (2.6), 24 (2.7), 35 (4.2), 36 (0.8)
k
(0.187)
O
a Products obtained in a cold trap.
b Products obtained as cell drainings.
c Arranged in order of the elution time on GC.

232
T. Abe et al. / Journal of Fluorine Chemistry 97 (1999) 229±237
Scheme 5.
Scheme 6.
31 was obtained as the principal product from the ECF of
methyl (N,N-diethylamino)acetate [3].
cleavage of the C±O bond ꢁ to the carbonyl group resulted
in the increased amount of the F-tertiary amine formation
having the same number of carbon atoms as the parent
aminoalcohols. For example, from the ¯uorination of 9,
the following products were formed in a ratio of
20:(35‡36)ˆ4.5:5.0, depending on the position of the bond
scission (Scheme 6).
In order to examine the possibility for the suppression of
the formation of carbonium ions from 1 and 2 in AHF, the
ECF of the trimethylsilyl ethers 5 and 8, methyl carbonates 6
and 9, and bis carbonate 8 were examined (Runs 5ꢀ8 in
Table 1).
It has been demonstrated that the following general
reactions take place when alkylsilanes such as methyl
In Table 2, the results of the ¯uorination of 2-pyrrolidi-
noethanol (10), 2-morpholinoethanol (11), 2-piperidi-
noethanol (12), 2-piperazinoethanol (13) and the
silylether derivatives of 10 and 11 (namely 14 and 15)
are summarized.
trichlorosilane,
trimethyl
chlorosilane,
dimethoxy
dimethylsilane, and phenyl trichlorosilane were treated with
AHF at room temperature:
In the case of the ¯uorination of 2-(c-alkylamino)ethanols
10ꢀ13, good yields of the corresponding F-acid ¯uorides
were obtained (Runs 1ꢀ3) except for 13. Thus, by the
¯uorination of 10±12, F-pyrrolidioacetyl ¯uoride (37),
F-morpholinoacetyl ¯uoride (38), and F-piperidinoacetyl
¯uoride (39) were obtained in yields of 19.2%, 25.2% and
15.9%, respectively; these yields were found to be compar-
able to those obtained by the ECF of the corresponding
methyl esters of c-alkylamino-substituted acetic acid [4].
The major reason would be ascribed to the fact that the
elimination of the OH group from the starting 2-(c-alkyla-
mino)ethanol occurred to a small extent, which was revealed
by the relatively small amounts of F-N-ethylcyclicamines
formed having the same number of carbon atoms as that of
starting 2-(c-alkylamino)ethanols [for example, F-N-ethyl-
pyrrolidine (40) and F-N-ethylmorpholine (41) were
obtained from 10 and 11 in yields of 3.2% and 2.9%,
respectively]. Furthermore, intermolecular condensation
did not take place in these cases, as the formation of the
F-linear ethers represented by RfCF2CF2OCF2CF2Rf
(Rf=F-c-alkylamino group) was not observed in the pro-
ducts from 10±12.
1. most Si±O bonds cleave to form Si-F bonds;
2. Si±C bonds cleave to form Si±F bonds, but only to a very
minor extent; and
3. all Si±Cl bonds change into Si±F2.
In the ECF of trimethylsilyl ethers 5 and 8, it was found
that products contain a considerable quantity of trimethyl-
¯uorosilane, which showed a facile Si±O bond cleavage
during ECF. However, the yields and the distribution of the
products excluding the formation of timethyl¯uorosilane
were very similar to those obtained from 1 and 2. Thus, the
yields of expected F-acid ¯uorides 19 and 20 could not be
improved as compared with the results of ECF of 1 and 2,
respectively (Runs 5 and 8).
In the case of ¯uorination of methyl carbonates 6 and 9
and bis-2-(N,N-dimethylamino)ethyl carbonate (7), the
yields of the corresponding F-acid ¯uorides 19 and 20
decreased as compared with those obtained from 1 and 2
[yields of 19: 7.3% (from 6) and 12.8% (from 7); yield of 20:
4.5% (from 9)] (Runs 6, 7 and 9). These results possibly
indicate that the cleavage of both C±O bonds of the ester
functional group occurred to an almost equal extent. The
Although the formation of 1-¯uorocarbonyldi¯uoro-
methyl-4-¯uoro-octa¯uoropiperazine (41) from 13 was
expected upon considering the similarity in the ¯uorination
2It has been shown that alkylsilanes afforded only C-Si bond cleavage
products when they were subjected to ECF; see Ref. [14]

T. Abe et al. / Journal of Fluorine Chemistry 97 (1999) 229±237
233
Table 2
Results of the fluorination of 10±15
aProducts obtained in a cold trap.
bProducts obtained as cell drainings.
cArranged in order of the elution time on GC.
of N-methylpiperadine3, compound 41 was not detected.
Instead, Compound 32 was obtained as a result of the
scission of the C±N bond at the site of the secondary imino
group. Interestingly, the formation of 31, which is a different
heterocyclic compound from the starting 13, was also
observed as the cyclization product; this indicates that
the cleavage of the C±N bond at the site of the imine occurs
at an early stage of ¯uorination (Scheme 7).
The ¯uorination of the trimethylsilyl ethers 14 and 15
were conducted in a manner similar to the ¯uorination of 5
and 8. It was found that the yields of the desired F-acid
¯uorides 37 and 38 were slightly improved as compared
with the results obtained from 10 and 11, respectively. The
ECF of 2-(N,N-dialkylamino)ethanols is a useful method for
preparing F-N,N-dialkylaminoacetyl ¯uorides, particularly
those having a F-c-alkylamino group. With respect to the
starting material for the synthesis of F-(c-alkylamino)acetyl
¯uoride by ECF, the use of 2-(c-alkylamino)ethanol, which
is available commercially as a bulk material, has an advan-
tage over the known method using methyl esters of
c-alkylamino-substituted acetic acid [4].
3. Experimental
Boiling points were uncorrected. The 2-(N,N-dialkylami-
no)ethanols (1), 3-(N,N-dimethylamino)propanol (2) and 4-
(N,N-dimethylamino)butanol (3) were used as commercial
grade. Trimethylsilyl ethers of 1, 2, 2-pyrrolidinoethanol
3It has been shown that the corresponding 1-trifluoromethyl-4-fluoro-
octafluoropiperazine was obtained by the ECF of N-methylpiperazine in
6.8% yield; see Ref. [15].

234
T. Abe et al. / Journal of Fluorine Chemistry 97 (1999) 229±237
Scheme 7.
(10), and 2-morpholinoethanol (11) were prepared by the
reaction of corresponding aminoalcohols with hexamethyl-
disilazane following the method described in the literature
[16]. The methyl carbonates of 1 and 2, and bis-2-(N,N-
dimethylamino)ethyl carbonate (7) were prepared by the
reaction of the corresponding amino alcohols with dimethyl
carbonate in the presence of Na following the methods
described in the literature [17]. The substrates synthesized
for ¯uorination had the following boiling points: 2-(N,N-
dimethylamino)ethyl trimethylsilyl ether (5), bp 51ꢀ538C/
20 mmHg; 2-(N,N-dimethylamino)ethyl methyl carbonate
(6), 67ꢀ698C/13 mmHg; bis-(2-N,N-dimethylaminoethyl)
carbonate (7), 82ꢀ858C/4 mmHg; 3-(N,N-dimethylamino)-
propyl trimethylsilyl ether (8), bp 708C/12 mmHg; 3-(N,N-
dimethylamino)propyl methyl carbonate (9), 66ꢀ678C/
20 mmHg; 2-pyrrolidinoethyl trimethylsilyl ether (14), bp
75ꢀ768C/12 mmHg; and 2-morpholinoethyl trimethylsilyl
ether (15), bp 578C/2 mmHg. Purity of anhydrous hydrogen
¯uoride (AHF) (Daikin Industries) was more than 99.8%.
The electrolytic ¯uorination apparatus and operating pro-
cedures were similar to those described previously [1,2].
Analytical GLC work was carried out with a Shimadzu GC-
14B gas chromatograph using stainless columns (3 mm
diameter) packed with 25% Fomblin YR on Chromosorb
PAW (6.4 m). For semi-preparative work, a GASUKURO
LL-75 modi®ed gas chromatograph using stainless columns
(10 mm diameter) packed with 30% KelF wax on Chromo-
sorb PAW (4.9 m), and a Varian model 920 GC using an
aluminum column (3/8 inch diameter) packed with 20% KF-
96 on Chromosorb PAW (20 feet) were used. The carrier gas
was helium in all cases. Infrared spectra were measured on a
Shimadzu FTIR-8000PC spectrometer using a 6 cm gas cell
with KBr windows. 19F NMR spectra were measured on a
Varian Unity Inova 300 spectrometer (282.238 MHz for 19F
density of 2.9 A/dm2, a cell voltage of 5.9ꢀ6.2 V, and a cell
temperature of 7ꢀ88C over a period of 744 min (274 Ahr).
Atthe®nalstageofthe¯uorination,thevoltagereached6.7 V.
The ef¯uent gases from the cell were passed over NaF
pellets and then condensed in a trap cooled to 788C. The
gaseous products which did not condense in the 788C trap
were then bubbled through a ¯uoropolymer bottle contain-
ing water and a gas washing bottle containing an aqueous
solution of a mixture of K2CO3, KOH and KI. All products
except new ones were identi®ed by comparison of their
infrared spectra and GLC retention times with those of
authentic samples. New compounds were separated from
the other products by use of semi-preparative GLC, and their
structures were determined on the basis of their IR,
19F NMR and mass spectra.
The products (27.9 g) condensed in the 788C trap
consisted of F-trimethylamine (22) (3.5 g), N,N-bis(tri¯uoro-
methyl)di¯uoromethylamine (23) (1.9 g), F-N,N-dimethyl-
ethylamine (24) (1.5 g), F-N,N-dimethylaminoacetyl
¯uoride (19) [3] (13.8 g), and unidenti®ed products
(7.2 g). Cell drainings (1.9 g) consisted of F-bis-2-(N,N-
dimehtylamino)ethyl ether (25) [18] (1.8 g) and unidenti®ed
products (0.1 g). The yield of 19 was 12.5%.
Compound 19 was derivatized into an amide of p-meth-
oxyaniline for further characterization: into a 100 ml poly-
tetra¯uoroethylene beaker, was placed 3.69 g (0.03 mol) of
p-methoxyaniline dissolved in 20 ml of dichloromethane
and 10.1 g (0.1 mol) of triethylamine, and a portion (2.49 g)
of product collected at 788C trap was added dropwise
while shaking. The mixture was left standing in the draft
overnight. The residue was dissolved in a mixture of hexane
and acetonitrile (1:1) and analyzed by TLC. The crude
product was puri®ed by column chromatography (hexane/
acetonitrile as eluent) to give F-(N,N-dimethylaminoace-
tyl)-p-methoxyanilide as white crystals (0.64 g, 56% yield).
F-(N,N-dimethylaminoacetyl)-p-methoxyanilide (nc):
m.p. 106ꢀ1078C. IR (KBr disk): 1705 ꢂ(C=O), 1544 (s),
1518 (ms), 1417ꢀ1313 (vs), 1263 (v), 1200ꢀ1184 (vs),
1101 (s), 1039 (m), 988 (s), 947 (ms), 883 (m), 829 (ms),
817 (ms), 770 (w), 741 (w), 19F NMR (CDCl3): ꢃ 53.9 (t,
6F, JF-Fˆ10.4 Hz, CF3), ꢃ 88.0 (quintet, 2F, JF-Fˆ10.4 Hz,
NCF2). 1H NMR: ꢃ 7.84 (s, 1H, NH), ꢃ 7.45 (d, 2H), ꢃ 6.90
1
and 299.95 MHz for H, respectively). Chemical shifts for
19F and 1H NMR spectra were reported respective to CFCl3
and TMS, respectively. Positive shifts are down®eld from
the reference (CFCl3 and TMS). Mass spectra were mea-
sured on a Shimadzu GC/MS-QP5000 instrument ®tted with
a capillary column (Neutra Bond-1, 30 m long, 0.25 ID,
1.5 mm thick) at 70 eV.
‡
3.1. Fluorination of 2-(N,N-dimethylamino)ethanol (1)
(s, 2H), ꢃ 3.81 (s, 3H, OCH3). MS: 353 (M‡1 , 4.2), 352
‡
‡
‡
‡
(M , 39.9), 150 (C8H8NO2 , 10.4), 149 (C8H7NO2 , 100),
‡
‡
Sample 1 (39.5 g, 0.443 mol) was charged into a cell
containing 450 ml electrically puri®ed AHF, and the solu-
tion was subjected to ¯uorination with an anodic current
122 (C7H8NO2 , 38.2), 114 (C2F4N , 13.1), 69 (CF3 , 28.6).
The physical properties and spectral data for 25 are
shown, as no data are given in the literature [18].

T. Abe et al. / Journal of Fluorine Chemistry 97 (1999) 229±237
235
F-bis-2-(N,N-dimethylamino)ethyl ether (25): bp
105ꢀ1078C, n2D0 < 1:28, and d420 1.7934. IR (capillary ®lm):
1300ꢀ1380 (vs), 1269 (v), 1200ꢀ1265 (vs), 1134 (s), 1196
(ms), 991 (s), 989 (m), 928 (s), 901 (s), 768 (m), 731 (s).
19F NMR (CDCl3): ꢃ 53.1 (t, 3F, JF-Fˆ15.5 Hz, CF3), ꢃ
96.5 (sept., 2F, JF-Fˆ15.5 Hz, NCF2), ꢃ 86.9 (m, 2F,
90.8 (m, 2F, NCF2), ꢃ 124.8 (m, 2F, ±CF2±). Mass: 302
‡
‡
(ꢁCF3†2NCF2CF2CF2 , 2.4), 252 (C4F10N , 0.2), 214
‡
‡
‡
‡
(C4F8N , 19.2), 202 (C3F8N , 34.7), 169 (C3F7N ,
‡
‡
13.3), 119 (C2F5 , 2.0), 114 (C2F4N , 62.2), 100 (C2F4 ,
‡
‡
11.7), 69 (CF3 , 100), 50 (CF2 , 2.0).
‡
±OCF2±). Mass: 252 (ꢁCF3†2NCF2CF2 , 3.6), 202
3.3. Fluorination of methyl 4-(N,N-dimethylamino)butanol
(3)
‡
‡
‡
‡
(ꢁCF3†2NCF2 , 39.7), 164 (C3F6N , 26.3), 119 (C2F5 ,
‡
‡
32.7), 114 (C2F4N , 69.9), 100 (C2F4 , 8.5), 69 (CF3 ,
‡
100), 50 (CF2 , 3.6).
Sample 3 (39.6 g, 0.338 mol) was ¯uorinated similarly
under the following conditions; 2.9 A/dm2, 6.2ꢀ6.3 V,
7ꢀ88C, 652 min (246 Ahr). The work-up gave the following
products in the 788C trap (26.2 g): F-propionyl ¯uoride
(5.0 g), F-butyryl ¯uoride (29) (12.5 g), 35 (2.2 g), F-N,N-
dimethyl-n-butylamine (30) (0.6 g), F-3-N,N-dimethylami-
nobuturyl ¯uoride (21) (1.4 g) and unidenti®ed products
(4.5 g). Cell drainings (0.8 g): all unidenti®ed products. The
yield of 21 was 1.2%.
3.2. Fluorination of 3-(N,N-dimethylamino)propanol (2)
Sample 2 (39.8 g, 0.386 mol) was ¯uorinated similarly
under the following conditions: 2.9 A/dm2, 5.9ꢀ6.2 V,
7ꢀ88C, 675 min (251 Ahr). The work-up gave the following
products in the 788C trap (23.1 g): 22 (1.9 g), 23 (2.5 g),
24 (3.1 g), N-di¯uoromethyl-N-tri¯uoromethylpenta¯uoro-
ethylamine (42) (1.1 g), F-N,N-dimethyl-N-propylamine
(35) (1.7 g), F-2-(N,N-dimethylamino)propionyl ¯uoride
(20) (6.2 g) [3], N-di¯uoromethyl-N-tri¯uoromethyl-n-hep-
ta¯uoropropoylamine (36) (1.1 g), and unidenti®ed pro-
ducts (5.5 g). Cell drainings (4.8 g): F-3-(N,N-
dimethylamino)propyl F-ethyl ether (27) (0.3 g), F-3-
(N,N-dimethylamino)propyl F-propyl ether (28) (1.1 g),
F-bis(3-N,N-dimethylaminopropyl) ether (26) (2.8 g), uni-
denti®ed products (0.6 g). The yield of 20 was 5.3 mol%.
F-3-(N,N-dimethylamino)propyl F-ethyl ether (27) (nc):
bp 75ꢀ788C. IR (capillary ®lm): 1320ꢀ1365 (vs),
1180ꢀ1260 (vs), 1148 (vs), 1101 (ms), 991 (vs), 860 (s),
755 (s), 729 (ms). 19F NMR (CDCl3): d 52.9 (m, 6F, N-
CF3), ꢃ 84.0 (m, 2F, ±CF2O±), ꢃ 87.3 (s, 3F, CF3), ꢃ
88.9(m, 2F, ±OCF2±), ꢃ 91.4(m, 2F, ±NCF2±), ꢃ 125.4
F-3-(N,N-dimethylamino)butyryl ¯uoride (21) (nc): IR
(gas): 1888 ꢂ(C=O) (ms), 1360 (vs), 1340 (s), 1231 (vs),
1175 (m), 1136 (m), 1074 (w), 995 (ms), 845 (w), 730 (w).
Further characterization of 21 was conducted in the form of
the methyl ester. Methyl F-3-(N,N-dimethylamino)butyrate
(46) was prepared by mixing about 2 g of the products
( 788C trap) with 1 ml of methanol. The reaction was
completed within a few minutes. The lower layer of the
reaction mixture was then separated and subjected to semi-
preparative GLC to give pure 46. Methyl F-3-(N,N-
dimethylamino)butyrate (46) had bp 62ꢀ638C. IR (capil-
lary ®lm): 1794 ꢂ(C=O). 19F NMR (CDCl3): ꢃ 52.9 (t, t, t,
3F JF-Fˆ15.5, 8.4 Hz, CF3), ꢃ 90.8 (m, 2F, NCF2), ꢃ
119.2 (t, 2F JF-Fˆ12.1 Hz, ±CF2±), ꢃ 122.6 (m, 2F,
‡
‡
CF2C(O)OMe). Mass: 342 ([M-F] , 0.5), 214 (C4F8N ,
‡
‡
‡
‡
‡
‡ ‡
4.0), 209 (C5H3F6O2 , 14.0), 202 (C3F8N , 7.7), 181 (C4F7 ,
(m, 2F, ±CF2±). Mass: 418 ([M-F] , 0.1), 330 (C6F15NO ,
‡
‡ ‡
‡
3.0), 169 (C3F7N , 5.5), 164 (C3F6N , 1.5), 150 (C3F6 ,
‡
0.3), 280 (C5F13NO , 0.3), 219 (C4F9 , 0.4), 214 (C4F8N ,
‡
‡
‡
‡ ‡
6.3), 109 (C3H3F2O2 , 2.0), 119 (C2F5 , 10.4), 114 (C2F4N ,
4.4), 202 (C3F8N , 11.7), 169 (C3F7N , 8.7), 164 (C3F6N ,
‡
‡
‡
‡
‡
‡
2.8), 147 (C3F5O , 2.0), 131 ꢁC3F5 , 0.8), 119 (C2F5 , 30.7),
25.0), 100 (C2F4 , 16.0), 69 (CF3 , 74.5), 59 (CO2Me , 100).
‡
‡
‡
114 (C2F4N , 27.9), 100 (C2F4 6.8), 69 (CF3 , 100), 50
‡
‡
(CF2 , 3.4), 47 (COF , 1.4).
3.4. Fluorination of 2-(N,N-diethylamino)ethanol (4)
F-3-(N,N-dimethylaminopropyl) F- propyl ether (28)
(nc): bp 85ꢀ878C. IR (capillary ®lm): 1315ꢀ1370 (vs),
1190ꢀ1260 (vs), 1150 (va), 991 (vs), 860 (vs), 759 (s), 724
(s). 19F NMR: (CDCl3) d 52.4 (t,t, 6F, JF-Fˆ15.5, 8.7 Hz,
N-CF3), ꢃ 81.3 (t, 3F, JF-Fˆ6.8 Hz, CF3), ꢃ 83.2 (m, 2F,
±CF2O±), ꢃ 84.1 (m, 2F, ±OCF2±), ꢃ 90.6 (m, 2F, NCF2),
Sample 4 (40.3 g, 0.344 mol) was ¯uorinated similarly
under the following conditions: 2.9 A/dm2, 6.06.3 V,
7ꢀ88C, 729 min (275 Ahr). The work-up gave the following
products in the 788C trap (19.8 g): 33 (3.6 g), 34 (3.8 g),
F-N-ethylmorpholine (31) (4.5 g), F-(N,N-diethylamino)-
acetyl ¯uoride (32) [3] (3.6 g), and unidenti®ed products
(4.3 g). Cell drainings (25.4 g): 33 (1.4 g), 34 (4.2 g), 31
(9.3 g), 32 (7.1 g), and unidenti®ed products (3.4 g). The
yield of 32 was 9.0%.
ꢃ
468 ([M-F] , 0.1), 380 (C7F17ON , 0.4), 302
124.6 (m, 2F, ±CF2±), ꢃ 129.8 (m, 2F, ±CF2±). Mass:
‡
‡
‡
‡
(ꢁCF3†2NCF2CF2CF2 , 0.8), 214 (C4F8N , 9.3), 202
‡
‡
‡
(C3F8N , 15.0), 169 (C3F7N , 36.9), 147 (C3F5O , 1.5),
‡
‡
‡
119 (C2F5 , 8.0), 114 (C2F4N , 35.2), 100 (C2F4 , 9.8), 69
‡
‡
‡
(CF3 , 100), 50 (CF2 , 2.9), 47 (COF , 1.3).
3.5. Fluorination of 2-(N,N-dimethylamino)ethyl
trimethylsilyl ether (5)
F-bis-3-(N,N-dimethylamino)propyl ether (26) (nc): bp
113ꢀ1158C, n2D01:2803; d420 1.8260. IR (capillary ®lm):
1310ꢀ1260 (vs), 1150 (vs), 991 (vs), 860 (s), 759 (s),
724 (s). 19F NMR (CDCl3): ꢃ 52.6 (t,t, 3F, JF-Fˆ15.5,
8.7 Hz, N-CF3), ꢃ 83.4 (t, 2F, JF-Fˆ5.1 Hz, CF2O ), ꢃ
Sample 5 (31.6 g, 0.196 mol) was ¯uorinated similarly
under the following conditions: 2.9 A/dm2, 5.7ꢀ6.7 V,
7ꢀ88C, 521 min (172 Ahr). The work-up gave the following

236
T. Abe et al. / Journal of Fluorine Chemistry 97 (1999) 229±237
products in the 788C trap (19.8 g): 24 (0.6 g), 19 (3.9 g),
and unidenti®ed products (15.3 g). The yield of 19 was
8.1%.
into an amide of p-methoxyaniline for further characteriza-
tion. The procedure is the same as explained for the pre-
paration of that of 19. Thus, a portion (3.11 g) of Cell
drainings was reacted with 3.69 g of p-methoxyaniline in
the presence of 10.1 g of triethylamine. After the removal of
solvent, the residue was chromatographed (hexane/acetoni-
trile as eluent) to give F-(N-pyrrolidinoacetyl)-p-methox-
yanilide as white crystals (1.07 g, 46% yield).
3.6. Fluorination of 2-(N,N-dimethylamino)ethyl methyl
carbonate (6)
Sample 6 (30.2 g, 0.206 mol) was ¯uorinated similarly
under the following conditions: 2.9 A/dm2, 5.9ꢀ7.0 V,
7ꢀ88C, 587 min (176 Ahr). The work-up gave the following
products in the 788C trap (8.6 g): 22 (0.9 g), 23 (0.4 g), 24
(1.9 g), 19 (3.7 g), and unidenti®ed products (1.7 g). The
yield of 19 was 7.3%.
N-(pyrrolidinoacetyl)-p-methoxyanilide (nc); m.p.114ꢀ
1158C. IR (KBr disk): 1701 ꢂ(C=O), 1543 (ms),
1470ꢀ1339 (vs), 1313 (ms), 1264ꢀ1254 (vs), 1202 (vs),
1165 (vs), 1124 (s), 1103 (s), 1020 (ms), 968 (s), 876 (m),
820 (s), 800 (m), 694 (m). 19F NMR (CDCl3): d 87.3
(pentet, 2F, JF-Fˆ8.5 Hz, CF2C(O)), ꢃ -91.2 (triplet, 4F,
1
3.7. Fluorination of bis(2-N,N-dimethylaminoethyl)
carbonate (7)
JF-Fˆ8.5 Hz, NCF2), ꢃ 132.9 (s, 4F, CF2). H NMR: d
7.96 (s, 1H, NH), ꢃ 7.49 (d, 2H), ꢃ 6.92 (s, 2H), ꢃ 3.82 (s, 3H,
‡
‡
OCH3). MS: 415 ([M‡1] , 5.3), 414 (M , 37.2), 264
‡
‡
‡
Sample 7 (26.0 g, 0.148 mol) was ¯uorinated similarly
under the following conditions: 2.9 A/dm2, 5.7ꢀ7.0 V,
7ꢀ88C, 510 min (176 Ahr). The work-up gave the following
products in the 788C trap (13.4 g): 22 (1.1 g), 23 (0.6 g),
24 (4.9 g), 19 (4.7 g), and unidenti®ed products (2.1 g). The
yield of 19 was 12.8%.
(C5F10N , 7.4), 150 ꢁC8H8NO2 , 10.7), 149 ꢁC8H7NO2 ,
‡ ‡
‡
100), 122 (C7F8NO , 40.4), 114 (C2F4N , 5.9), 78 (C6H6 ,
‡
‡
3.9), 69 (CF3 , 14.6), 64 (CF2N , 3.6).
3.11. Fluorination of 2-morpholinoethanol (11)
Sample 11 (38.2 g, 0.291 mol) was ¯uorinated similarly
under the following conditions; 2.9 A/dm2, 6.0ꢀ6.1 V,
7ꢀ88C, 627 min (228 Ahr). The work-up gave the following
products in the 788C (20.6 g): F-diethylether (8.8 g), F-N-
methylmorpholine (45) (6.5), F-N-ethylmorpholine (31)
(0.5 g), F-morpholinoacetyl ¯uoride (38) (2.8 g), and uni-
denti®ed products (2.0 g). Cell Drainings (28.1 g): (45)
(4.0 g), 31 (2.4 g), 38 (21.2 g), and unidenti®ed products
(0.4 g). The yield of 38 was 25.2%.
3.8. Fluorination of 3-(N,N-dimethylamino)propyl
trimethylsilyl ether (8)
Sample 8 (35.0 g, 0.200 mol) was ¯uorinated similarly
under the following conditions: 2.9 A/dm2, 5.9ꢀ6.6 V,
7ꢀ88C, 674 min (213 Ahr). The work-up gave the following
products in the 788C (22.1 g): 24 (1.6 g), 35 (1.1 g), 20
(3.2 g), and unidenti®ed products (16.2 g). Cell drainings
(3.7 g): 27 (0.6 g), 28 (1.5 g), 26 (1.2 g), and unidenti®ed
products (0.4 g). The yield of 20 was 6.1%.
3.12. Fluorination of 2-piperidinoethanol (12)
3.9. Fluorination of 3-(N,N-dimethylamino)propyl methyl
carbonate (9)
Sample 12 (40.9 g, 0.317 mol) was ¯uorinated similarly
under the following conditions: 2.9 A/dm2, 5.7ꢀ6.1 V,
7ꢀ88C, 664 min (251 Ahr). The work-up gave the following
products in the 788C trap (20.9 g): 43 (1.6 g), F-pentane
(47) (13.1 g), F-N-methylpiperidine (48) (3.5 g), and uni-
denti®ed products (2.7 g). Cell drainings (30.4 g); 47
(0.7 g), 48 (5.6 g), F-piperidinoacetyl ¯uoride (39) (16.3),
and unidenti®ed products (7.8 g). The yield of 39 was
15.9%.
Sample 9 (30.1 g, 0.187 mol) was ¯uorinated similarly
under the following conditions: 3.3 A/dm2, 5.7ꢀ6.8 V,
7ꢀ88C, 504 min (179 Ahr). The work-up gave the following
products in the 788C (9.8 g): 22 (0.6 g), 23 (1.0 g), 24
(1.4 g), 35 (2.5 g), 20 (2.5 g), 36 (0.5 g), and unidenti®ed
products (1.3 g). The yield of 20 was 4.5%.
Compound 39 was derivatized into an amide of p-meth-
oxyaniline for further characterization. The procedure is the
same as explained for the preparation of that of 19. Thus, a
portion (3.69 g) of cell drainings was reacted with 3.69 g of
p-methoxyaniline in the presence of 10.1 g of triethylamine.
After the solvent was evaporated, the residue was chroma-
tographed (hexane/acetonitrile as eluent) to give F-(piper-
idonoacetyl)-p-methoxyanilide as white cryatals (1.19 g,
49% yield).
3.10. Fluorination of 2-pyrrolidinoethanol (10)
Sample 10 (33.3 g, 0.289 mol) was ¯uorinated similarly
under the following conditions: 2.9 A/dm2, 5.9ꢀ6.0 V,
7ꢀ88C, 571 min (211 Ahr). The work-up gave the following
products in the 788C, (25.9 g): 43 (7.6 g), F-N-methyl-
pyrrolidine (44) (11.2), F-N-ethylpyrrolidine (40) (0.8 g),
F-pyrrolidinoacetyl¯uoride (37) (4.3 g), and unidenti®ed
products (2.0 g). Cell drainings (21.0 g): 44 (2.2 g), 40
(2.4 g), 37 (15.0 g), and unidenti®ed products (1.4 g).
The yield of 37 was 21.4%. Compound 37 was derivatized
F-(piperidonoacetyl)-p-methoxyanilide
(nc):
m.p.
116ꢀ1188C; IR (KBr disk): 1707 ꢂ (C=O), 1541 (m),
1365ꢀ1346 (s), 1309 (s), 1263 (s), 1234 (s), 1186 (vs),

T. Abe et al. / Journal of Fluorine Chemistry 97 (1999) 229±237
237
1146 (vs), 1088 (m), 1012 (ms), 965 (s), 888 (w), 827 (ms),
804 (w). 19F NMR (CDCl3): ꢃ 83.6 (pentet, 2F, JF-F
7ꢀ88C, 808 min (288 Ahr). The work-up gave the following
products in the 788C trap (20.3 g): 44 (6.9), 40 (1.5 g), 37
(4.5 g), and others (7.4 g). Cell drainings (20.1 g): 44
(1.8 g), 40 (3.1 g), 37 (11.2 g), and unidenti®ed products
(4.0 g). The yield of 37 was 23.6%.
ˆ
17.2 Hz, CF2C(O)), ꢃ 91.7 (t, 4F, JF-Fˆ17.2 Hz, NCF2), ꢃ
1
131.8 (m, 4F, CF2), ꢃ 134.1 (m, 2F, CF2). H NMR: ꢃ
7.89 (s, 1H, NH), ꢃ 7.46 (d, 2H), ꢃ 6.91 (s, 2H), ꢃ 3.01 (s, 3H,
‡
‡
OCH3). MS: 465 ([M‡1] , 4.0), 464 (M , 26.5), 150
‡
‡
‡
(C8H8NO2 , 11.4), 149 (C8H7NO2 , 100), 122 (C7H8NO2 ,
‡
3.15. Fluorination of 2-morpholinoethyl
trimethylsilylether (15)
‡
‡
40.3), 119 (C2F5 , 6.1), 114 (C2F4N , 6.5), 78 C6H6 , 2.8),
‡
‡
‡
69 (CF3 , 17.3), 64 (CF2N , 3.6), 50 (CF2 , 4.2).
Sample 15 (35.9 g, 0.177 mol) was ¯uorinated similarly
under the following conditions; 2.9 A/dm2, 6.0ꢀ6.1 V,
7ꢀ88C, 614 min (229 Ahr). The work-up gave the following
products in the 788C trap (20.2 g): 45 (5.4 g), 31 (0.7 g),
38 (5.1 g), and unidenti®ed (9.0 g). Cell drainings (19.2 g):
45 (3.1 g), 31 (1.8 g), 38 (14.2 g), and unidenti®ed products
(0.1 g). The yield of 38 was 33.5%.
3.13. Fluorination of 2-piperazinoethanol (13)
Sample 13 (41.2 g, 0.317 mol) was ¯uorinated similarly
under the following conditions; 2.9 A/dm2, 6.0ꢀ6.4 V,
7ꢀ88C, 616 min (229 Ahr). The work-up gave the following
products in the 788C trap (21.9 g): 33 (6.0 g), 34 (1.4 g),
31 (2.3 g), 32 (7.8 g), and unidenti®ed products (4.4 g). Cell
drainings (4.3 g): 33 (0.3 g), 34 (0.4 g), 31 (1.2 g), 32
(1.8 g), and unidenti®ed products (0.6 g). The formation
of 1-¯uorocarbonyldi¯uoromethyl-4-¯uoro-octa¯uoropi-
perazine (41) could not be con®rmed, but the yield of F-
N,N-diethylacetyl ¯uoride (32) was 8.7%. Compound 32
was derivatized into an amide of p-methoxyaniline for
further characterization. The procedure is the same as
explained for the preparation of that of 19. Thus, a portion
(3.49 g) of cell drainings was reacted with 3.69 g of p-
methoxyaniline in the presence of 10.1 g of triethylamine.
After removal of the solvent, the residue was chromato-
graphed (hexane/acetonitrile as eluent) to give F-(N,N-
diethylaminoacetyl)-p-methoxyanilide as white cryatals
(1.45 g, 76% yield).
References
[1] M. Howe-Grant (Ed.), Fluorine Chemistry: A Comprehensive
Treatment, Encyclopedia Preprint Series, Wiley, New York, 1995,
pp. 304±318.
[2] R.E. Banks, Fluorocarbons and Their Derivatives, MacDonald,
London, 1970, pp. 70±101.
[3] T. Abe, E. Hayashi, H. Baba, H. Fukaya, J. Fluorine Chem. 48 (1990)
257.
[4] T. Abe, E. Hayashi, H. Fukaya, H. Baba, J. Fluorine Chem. 50 (1990)
173.
[5] T. Abe, E. Hayashi, H. Fukaya, Y. Hayakawa, H. Baba, S. Ishikawa,
K. Asahino, J. Fluorine Chem. 57 (1992) 101.
[6] T. Abe, H. Fukaya, E. Hayashi, Y. Hayakawa, M. Nishida, H. Baba,
J. Fluorine Chem. 66 (1994) 193.
[7] T. Abe, H. Fukaya, T. Ono, E. Hayashi, I. Soloshonok, K. Okuhara,
J. Fluorine Chem. 87 (1998) 193.
F-(N,N-diethylaminoacetyl)-p-methoxyanilide (nc): m.p.
69ꢀ718C. IR (KBr disk): 1703 ꢂ(C=O), 1547 (ms), 1518
(m), 1355 (ms), 1298 (vs), 1259 (s), 1217 (vs), 1103 (vs),
1030 (m), 989 (w), 878 (ms), 818 (ms), 741 (m). 19F NMR
(CDCl3): ꢃ 82.2 (m, 6F, CF3), ꢃ 83.6 (m, 2F, NCF2), ꢃ
91.1 (m, 4F, CF2N). 1H NMR: ꢃ 7.95 (s, 1H, NH), ꢃ 7.44
(d, 2H), ꢃ 6.99 (s, 2H), ꢃ 3.80 (s, 3H, OCH3). MS: 453
[8] R.A. Guenthner, US Pat. 3 471 484 (1969).
[9] S. Nagase, R. Kojima, Bull. Chem. Soc., Jpn. 34 (1961) 1468.
[10] S. Nagase, R. Kojima, Kogyo Kagaku Zasshi, J. Chem. Soc., Jpn.,
Ind. Chem. Soc. 64 (1961) 1397.
[11] S. Nagase, H. Baba, R. Kojima, Bull. Chem. Soc., Jpn. 36 (1963)
29.
[12] T. Abe, S. Nagase, H. Baba, Bull. Chem. Soc., Jpn. 46 (1973)
2524.
‡
‡
‡
([M‡1] , 2.5), 352 (M , 17.1), 352 ([M-C2F4] , 3.6), 164
‡
‡
‡
(C3F6N , 5.1), 150 (C8H8NO2 , 10.6), 149 (C8H7NO2 ,
‡
[13] G.A. Olah, A.M. White, Chem. Rev. 70 (1970) 561.
[14] H. Yamaguchi, S. Nagase, H. Baba, K. Kodaira, Abstract of The First
Fluorine Conference of Japan, Tokyo, 1±2 November 1972, pp. 74±
76.
‡
100), 123 (C2F5N , 2.8), 119 (C2F5 , 16.9), 114
‡
‡
‡
‡
(C2F4N , 5.0), 78 (C6H6 , 2.6), 69 (CF3 , 12.1), 64 (CF2N ,
3.2).
[15] H. Baba, T. Abe, E. Hayashi, Nihon Kagaku Kaisi, J. Chem. Soc.,
Jpn. (1986) 1249.
3.14. Fluorination of 2-pyrrolidinoethyl trimethylsilylether
(14)
[16] C.A. Bruynes, T.K. Jurriens, J. Org. Chem. 47 (1982) 3966.
[17] P. Vieles, J. Galsomias, Bull. Chim. Soc. (1968) 461.
[18] G.G.I. Moore, J.C. Hansen, T.M. Barrett, J.E. Waddell, K.M. Jewell,
T.A. Kestner, R.M. Payfer, J. Fluorine Chem. 32 (1990) 41.
Sample 14 (40.1 g, 0.214 mol) was ¯uorinated similarly
under the following conditions; 2.9 A/dm2, 5.6ꢀ5.8 V,