Claisen rearrangements based on vinyl fluorides

Article abstract of DOI:10.1016/j.jfluchem.2004.09.001

2-Fluoroalk-1-en-3-ols (4), available from terminal alkenes (1) by bromofluorination, subsequent dehydrobromination of the 1-bromo-2-fluoroalkanes (2) to form 2-fluoroalkenes (3) and selenium dioxide mediated allylic oxidation with tert-butylhydroperoxide, undergo Johnson-Claisen rearrangement on treatment with trimethyl orthoacetate to give methyl 4-fluoroalk-4-enoates (7) in high yields. In contrast Ireland-Claisen rearrangement of 3-acetoxy-2-fluorodec-1-ene (9b) with triethylamine and TMSOTf in ether failed. Instead of the expected formation of a carboxylic acid, selective C-silylation of the α-position to the carboxyl group to form 14 occurred. However, Ireland-Claisen rearrangement was successful with corresponding chloroacetates 10 and propionates 11 of four 2-fluoroalk-1-en-3-ols (4) to give 2-chloro-4-fluoroalk- 4-enecarboxylic acids (15) or its 2-methyl derivatives 16, respectively, in moderate yields. These [3,3]-sigmatropic rearrangements are diastereoselective giving trans-configured double bonds, exclusively. Corresponding esters derived from (Z)-2-fluorocyclododec-2-enol (22), did rearrange to yield mixtures of diastereomers much less selectively. Also 2-fluorodec-2-enol (6), which was prepared by rearrangement of 2-fluoro-2-octyloxirane (5) with TMSOTf and triethylamine, was successfully applied as a starting material for [3,3]-sigmatropic rearrangements. The corresponding 3-(1-fluoroethenyl)alkanoic acid derivatives 17 and 18 were formed in moderate yield. 2-Fluoroalk-1-en-3-ol esters prepared in two steps from 2-fluoroalk-1-enes undergo Claisen rearrangements to form 2-substistuted 4-fluoroalk-4-enecarboxylic acids.

Full text of DOI:10.1016/j.jfluchem.2004.09.001

Journal of Fluorine Chemistry 125 (2004) 1593–1608
www.elsevier.com/locate/fluor
Claisen rearrangements based on vinyl fluorides
*
Frank Tranel, Gu¨nter Haufe
¨ ¨ ¨ ¨
Organisch-Chemisches Institut, Westfalische Wilhelms-Universitat Munster, Corrensstr. 40, D-48149 Munster, Germany
¨
Dedicated to Professor Gerd-Volker Roschenthaler on the occasion of his 60th birthday.
Available online 13 November 2004
Abstract
2-Fluoroalk-1-en-3-ols (4), available from terminal alkenes (1) by bromofluorination, subsequent dehydrobromination of the 1-bromo-2-
fluoroalkanes (2) to form 2-fluoroalkenes (3) and selenium dioxide mediated allylic oxidation with tert-butylhydroperoxide, undergo
Johnson-Claisen rearrangement on treatment with trimethyl orthoacetate to give methyl 4-fluoroalk-4-enoates (7) in high yields. In contrast
Ireland-Claisen rearrangement of 3-acetoxy-2-fluorodec-1-ene (9b) with triethylamine and TMSOTf in ether failed. Instead of the expected
formation of a carboxylic acid, selective C-silylation of the a-position to the carboxyl group to form 14 occurred. However, Ireland-Claisen
rearrangement was successful with corresponding chloroacetates 10 and propionates 11 of four 2-fluoroalk-1-en-3-ols (4) to give 2-chloro-4-
fluoroalk-4-enecarboxylic acids (15) or its 2-methyl derivatives 16, respectively, in moderate yields. These [3,3]-sigmatropic rearrangements
are diastereoselective giving trans-configured double bonds, exclusively. Corresponding esters derived from (Z)-2-fluorocyclododec-2-enol
(22), did rearrange to yield mixtures of diastereomers much less selectively. Also 2-fluorodec-2-enol (6), which was prepared by
rearrangement of 2-fluoro-2-octyloxirane (5) with TMSOTf and triethylamine, was successfully applied as a starting material for [3,3]-
sigmatropic rearrangements. The corresponding 3-(1-fluoroethenyl)alkanoic acid derivatives 17 and 18 were formed in moderate yield.
# 2004 Elsevier B.V. All rights reserved.
Keywords: Fluorinated allylic esters; Vinyl fluorides; [3,3]-Sigmatropic rearrangement; Claisen rearrangement; Stereochemistry; Carboxylic acid derivatives
1. Introduction
[11,12]), the Reformatsky [13,14], the ester enolate [15–
17], and the Ireland-Claisen rearrangements [18–20] should
be mentioned as some of the synthetically most useful
variants regularly applied with non-fluorinated compounds.
Many examples of sigmatropic rearrangements with
polyfluorinated compounds have also been described [21–
23]. Among others there are Ireland-Claisen rearrangements
with terminal difluorinated allylic esters [23–25], Johnson-
Claisen rearrangements of allylic alcohols with terminal
difluorinated double bonds [24–28], and Claisen rearrange-
ments of polyfluorinated allylvinyl ethers [29–35]. In
contrast, there is a relatively small number of examples
for rearrangements with monofluorinated olefins. As early as
in 1988 a one-pot cascade reaction of a Claisen and
subsequent Cope-rearrangement of a vinyl fluoride was
described [36].
Rearrangement reactions belong to the most frequently
applied transformations of carbon skeletons in organic
synthesis. Besides the Cope-rearrangement and its variants,
the classical Claisen-rearrangement of allylphenyl ethers
and particularly the aliphatic Claisen-rearrangements gained
a very important position [1,2]. These reactions proceed as
symmetry-allowed suprafacial thermal [3,3]-sigmatropic
rearrangements through the lowest energy chair-like, six-
membered transition states [3–5]. This allows to predict the
stereochemistry of the formed main product. Most
importantly, from the synthetic point of view, there were
developed plenty of variants of this type of rearrangement.
By way of example, the Carroll [6,7], the Johnson [8], the
Eschenmoser [9,10] (including the Overman variant
As a typical example for a classical aromatic Claisen
rearrangement, a fluorinated analogue of the anti-malaria
agent Bialamicol was synthesized from a fluorinated
* Corresponding author. Tel.: +49 251 833 3281; fax: +49 251 833 9772.
E-mail address: haufe@uni-muenster.de (G. Haufe).
0022-1139/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2004.09.001

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F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
Scheme 1.
Scheme 3.
Scheme 2.
allylphenyl ether in the presence of p-dimethylamino
pyridine (DMAP) (Scheme 1) [37].
Different examples of Johnson-Claisen rearrangements of
2-fluoroallylic alcohols by treatment with triethyl orthoace-
tate or triethyl orthopropionate in hot phenol leading to the
corresponding ethyl esters have been published by Allmen-
dinger et al. These transformations yielded 42–74% of the
corresponding esters (Scheme 2) [38].
Scheme 4.
m-chloroperbenzoic acid. Epoxidation of vinyl fluorides has
been described earlier by Elkik and Le Blanc [50] and
Schlosser and Michel [51,52]. On the other hand it is known
that non-fluorinated allylic alcohols can be prepared from
epoxides by deprotonation of the 3-position with strong
bases such as LDA or KOtBu through an E1cb mechanism
[53]. Applying these and several similar conditions to the
fluorinated epoxide 5 led to complicated mixtures of many
fluorinated and non-fluorinated compounds in all cases.
Alternatively, ring opening of epoxides by treatment with
electrophiles such as butyldimethylsilyl iodide [54] or
trimethylsilyl trifluoromethane sulfonates [55] in the
presence of weak bases such as triethylamine has been
described. Under the conditions shown in Scheme 5, the
epoxide 5 was rearranged to 6 in low yield.
Analogously, several examples of Johnson-Claisen
rearrangements involving 3-fluoroalk-2-enol derivatives
have been published by Percy and coworkers [28,39] and
similar reactions were used as key-step in syntheses of
nucleosides [40–42].
In the frame of our interest in synthetic applications of
vinyl fluorides, we discovered a simple and efficient access
to 2-fluoroallylic alcohols some years ago consisting of
bromofluorination of terminal alkenes [43,44], dehydro-
bromination of the formed 1-bromo-2-fluoroalkanes [45–
47] and SeO2-mediated allylic oxidation [48]. Now we
investigated the application of these fluorinated allylic
alcohols in different types of Claisen rearrangements.
The mechanism of this reaction is not clear yet, but it is
known that silyl iodides or silyl triflates with tertiary amines
form ammonium salts, which are less active silylation
reagents [56,57]. Probably these Lewis acids can activate the
2. Results and discussion
Our well-established three-step sequence [47] of bromo-
fluorination of 1-alkenes 1, leading to 92:8 mixtures of 1-
bromo-2-fluoroalkanes 2 and its regioisomers, HBr-elim-
ination from the bromofluorides and selective allylic
oxygenation of the vinyl fluorides 3 provided the desired
fluorinated allylic alcohols 4a–4c in 25–43% overall yield
(Scheme 3). 2-Fluoroallylic alcohol (4d) was prepared from
ammonium 2-fluoroacrylate (Scheme 4) [49].
Another fluorinated primary allylic alcohol, 2-fluorodec-
2-enol (6), was prepared from the epoxide 5, which was
accessible from 2-fluorodecene (3b) by epoxidation with
Scheme 5.

F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
1595
Scheme 6.
Table 1
Results of Johnson-Claisen rearrangement of fluorinated allylic alcohols 4
Scheme 8.
Alcohol
R1
Ester
Yield (%)
4a
4b
4c
4d
C3H7
7a
7b
7c
7d
96
84
81
0
The corresponding propionates 11 were synthesized by
treatment of 4 with propanoic acid in the presence of DCC/
DMAP (method B) similarly to a protocol independently
described by Neises and Steglich [59] and Hassner and
Alexanian [60].
C7H15
C13H27
H
Similarly, also 2-fluorodec-2-enol (6) was acylated with
chloroacetic anhydride in the presence of pyridine and a
catalytic amount of DMAP or with propanoic acid/DCC/
DMAP to give the corresponding chloroacetate 12 or the
propionate 13, respectively (Scheme 9).
At the beginning of our investigations only two examples
[36,39] of Ireland-Claisen rearrangements of allylic acetates
bearing a vinylic fluorine were described in literature. All
our attempts towards rearrangement of 9b under classical
conditions of Ireland [19] failed and besides the starting
material only complex mixtures of products were formed.
oxirane, which in the absence of nucleophiles is opened and
subsequently deprotonated in the b-position. The thus-
formed silylether could not be isolated, but acidic hydrolysis
led to the desired allylic alcohol 6. All attempts to increase
the yield of this reaction failed until now.
Having several fluorinated allylic alcohols in hand, we
investigated Johnson-Claisen rearrangements of these
compounds. Thus, the fluoroallylic alcohols 4a–4c were
refluxed with trimethyl orthoacetate in toluene in the
presence of a catalytic amount of propionic acid for 5 h to
give the corresponding trans-configured methyl 4-fluoroalk-
4-enecarboxylates 7a–7c in good to excellent yields
(Scheme 6, Table 1). In contrast, compound 4d did not
give any of the expected ester under these conditions and
heating with the orthoester in the absence of a solvent was
unsuccessful as well. The reasons for this failure are not
clear yet.
Also under the conditions of
a thermodynamically
controlled enolization [61,62] the expected product of the
Ireland-Claisen rearrangement was not formed. However,
under these conditions a selective C-silylation of the a-
carbon to the carbonyl group to form the a-silylated ester 14
was observed, though the transformation was not complete
(Scheme 10).
Under standard conditions, the reaction of 2-fluorodec-2-
enol (6) with trimethyl orthoacetate was very slow (6%
conversion of 6 after refluxing in toluene for 6 h). Therefore,
compound 6 was refluxed in neat triethyl orthoacetate for 5 h
to give the rearrangement product 8 in 39% yield (Scheme
7). Elongation of the reaction time led to side reactions and
did not improve the yield. Steric reasons and the formation
of a less stable terminal double bond might be responsible
for the low yield of the latter reaction.
Such a-silylations were already observed in literature,
particularly when TMSOTf was used instead of TMSCl [63].
Though, several Ireland-Claisen rearrangements have been
described [18,19], this type of reactions seem not generally
to be possible with acetates and several failures of such
The fluorinated allylic alcohols 4 were subsequently
esterified by treatment with acetic anhydride or chloroacetic
anhydride, in the presence of DMAP (method A) according
Scheme 9.
¨
to a protocol developed by Steglich and Hofle [58] to
give the corresponding esters 9, 10 or 11, respectively
(Scheme 8).
Scheme 7.
Scheme 10.

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F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
Scheme 11.
Table 2
Synthesis of fluorinated allylic esters and 4-fluoroalk-4-enecarboxylic acid derivatives
Alcohol
R1
R2
X
Allylic ester (method)
Yield (%)
Carboxylic acid
Yield (%)
a
4b
4a
4b
4c
4d
6
4a
4b
4c
4d
6
C7H15
C3H7
C7H15
C13H27
H
H
H
9b (A)
91
79
92
95
84
99
68
90
74
50
94
–
0a
29
54
66
86
60
32
70
72
5
H
Cl
10a (A)
10b (A)
10c (A)
10d (A)
12 (A)
11a (B)
11b (B)
11c (B)
11d (B)
13 (B)
15a
15b
15c
15d
17
16a
16b
16c
16d
18
H
Cl
H
Cl
H
Cl
H
C7H15
H
Cl
C3H7
C7H15
C13H27
H
Me
Me
Me
Me
Me
H
H
H
H
C7H15
52
a
Ethyl ester formed by Johnson-Claisen rearrangement.
reactions have been mentioned in literature [26]. Since the
corresponding carboxylic esters are available by Johnson-
Claisen rearrangement, these investigations were not
continued.
competing deprotonation in b-position to the fluorine
substituent with strong bases. A comparable observation
was made by Percy et al. in rearrangements of Ireland-
Claisen systems bearing a g-fluorine substituent [39].
Therefore, we used another method of enolization acting
under less basic conditions and leading to the (Z)-enolate
under thermodynamic control. Thus, treatment of the esters
11 or 12 with TMSOTf and triethylamine at room
temperature in dichloromethane for 4 days gave the
expected 4-fluoroalk-4-enecarboxylic acids 15 or 16 bearing
a chlorine or a methyl substituent in 2-position in reasonable
yields (except compound 16d) (Scheme 11, Table 2).
From investigations of the crude product mixtures by GC
and 19F NMR spectroscopy it became obvious that the
reaction, after >80% conversion of starting material yielded
Furthermore, the esters 10 and 11 substituted by chlorine
or a methyl group in a-position to the carboxyl function
were treated with LDA and TMSCl using the classical
conditions of Ireland-Claisen rearrangement at À78 8C.
However, no rearrangement products were found after
warming the reaction mixture to room temperature. The
esters were partially recovered besides the allylic alcohols 4
produced by ester hydrolysis. Similar ester hydrolyses
initiated by silylation reagents have already been observed
for other types of reactions by Emde and Simchen [61].
Another reason for the failure of rearrangement might be a
Scheme 12.

F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
1597
exclusively the rearranged products 15 or 16, respectively.
The moderate yields are due to difficult isolation and
purification of the products, which were partially destroyed
during chromatographic separation (vide infra). Thus,
the Ireland-Claisen rearrangement gave the (Z)-configured
4-fluoroalk-4-enecarboxylic acids. This stereochemistry
becomes obvious from the big vicinal coupling constant
3JH,F of 37–38 Hz in the 1H NMR spectra of compounds 15
and 16.
The formation of these diastereomers can be rationalized
from the most probable transition state I (Scheme 12). The
alternative, II, with an axial R substituent is much less
probable. This type of stereocontrol was already described
by Ireland et al. [19].
The carboxylic acids 15b or 16b were treated with
methanol in the presence of DCC/DMAP to give the
corresponding methyl esters in 86 or 67% yield, respec-
tively.
Ireland-Claisen rearrangement of substituted carboxylic
esters of the primary allylic alcohol 2-fluorodec-2-enol,
namely the reactions of the chloroacetate 12 and the
propionate 13 under the same conditions gave mixtures of
diastereomers in 60 or 52% yield, respectively. Thus, from
12 a 1:1 mixture of compounds 17 was formed, while the
rearrangement of 13 led to a 81:19 mixture of the
diastereomers 18. These diastereomers were not separated
(Scheme 13, Table 2).
Scheme 14.
Scheme 15.
This type of an Ireland-Claisen rearrangement was much
less efficient starting with a cyclic vinyl fluoride derived
from (E)-cyclododecene (19) by bromofluorination and
subsequent HBr-elimination from the formed cis-1-bromo-
2-fluorocyclododecane (20) to form (E)-1-fluorocyclodode-
cene (21). The allylic oxidation with selenium dioxide and
tert-butylhydroperoxide occurred selectively in b-position
to the fluorine substituent to give the (Z)-configured allylic
alcohol 22 in low yield. The alcohol was esterified under the
conditions described above to give the esters 23 or 24 in
good yield.
chromatography was difficult and led to partial loss of
material. When about 10% of acetic acid was added to the
eluent, the vinyl moiety of compound 16b was partially
solvolyzed. We have shown earlier that this function is
sensitive against strong acids [48]. Thus, the ester 11b was
rearranged according to the general procedure and the crude
reaction product was subjected to column chromatography
(silica gel) using a mixture of cyclohexane, ethyl acetate and
acetic acid (10:1:1) as an eluent. In this way 2-methyl-4-
oxododecanoic acid (27) was isolated in 45% overall yield
(Scheme 15).
Ireland-Claisen rearrangement under the above-men-
tioned standard conditions gave the corresponding carboxylic
acids 25 or 26 in about 60% yields (GC) as about 70:30
mixtures of diastereomers (Scheme 14). The isomers could
neither be separated from each other nor from the starting
materials. Moreover, the formation of double bond isomers
could not be excluded.
3. Conclusion
It has been mentioned already that purification of the
4-fluoroalk-4-enecarboxylic acids 15 and 16 by column
Based on vinyl fluorides 3 and 21 a series of fluorinated
allylic alcohols 4, 6 and 22 has been synthesized. Refluxing
the allylic alcohols 4 or 6 with trimethyl- or triethyl
orthoacetate in toluene Johnson-Claisen rearrangement
occurred providing high-yielding access to (Z)-4-fluoroalk-
4-enecarboxylic esters 7 or 8, respectively. In agreement with
the behaviour of non-fluorinated allylic acetates, also
fluorinated analogues such as 3-acetoxy-2-fluorodec-2-ene
(9b) seem not to be suitable to undergo Ireland-Claisen
rearrangement on treatment with triethylamine and TMSOTf
at room temperature. Under these conditions, C-silylation of
Scheme 13.

1598
F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
the a-position to the carbonyl group occurred. On the other
hand, a-substituted acetates such as the a-chloroacetates 11
or the propionates 12 rearranged under the same conditions to
give the corresponding 2-substituted (Z)-4-fluoroalk-4-enoic
acids15or 16in moderateyields. The esters 23and 24derived
from (Z)-2-fluorocyclododec-2-enol (22) under similar
conditions gave mixtures of diastereomers in low yield.
The fluorovinylic moiety is hydrolysed to the keto group
under acidic conditions.
4.2.2. 1-Bromo-2-fluorodecane (2b)
According to the general procedure 2b was prepared from
1b (14.00 g, 0.1 mol). Yield: 22.76 g (95%) (contaminated
with 8% of the regioisomer and 3% of the 1,2-dibromide).
The spectroscopic data agree with those published in Ref.
[46].
4.2.3. 1-Bromo-2-fluorohexadecane (2c)
According to the general procedure 2c was prepared from
1c (22.40 g, 0.1 mol). Yield: 31.93 g (99%) (contaminated
with 8% of the regioisomer and 3% of the 1,2-dibromide).
1H NMR (CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 16-CH3),
1.26 (m, 22 H, 5-CH2–15-CH2), 1.35–1.55 (m, 2 H, 4-CH2),
4. Experimental
4.1. General remarks
1.60–1.80 (m, 2 H, 3-CH2), 3.46 (dd, 2JH,H = 5.0 Hz, 3JH,F
=
2
19.6 Hz, 2 H, 1-CH2), 4.61 (dm, JH,F = 47.7 Hz, 1 H, 2-
CHF). 13C NMR (CDCl3): d 14.1 (q, C-16), 22.7 (t, C-15),
24.7 (dt, 3JC,F = 3.8 Hz, C-4), 29.2–29.8 (t, C-5–C-13), 31.9
NMR spectra were recorded at 300 MHz (1H), 75 MHz
(13C) and 282 MHz (19F) and are reported in ppm downfield
from TMS (1H and 13C, CDCl3 as internal standard, d =
77.0 ppm), or CFCl3 (19F). Mass spectra were recorded by
GC/MS coupling (EI, 70 eV) or by GC/MS/CI (chemical
ionization). Gas chromatographic analyses were performed
using a column HP-5 (30 m, Ø0.32 mm, film 0.25 mm, carrier
gas N2) or SPB-1 (30 m, Ø0.32 mm, film 0.25 mm, carrier gas
N2). Thin-layerchromatography was done oncoated silicagel
plate Merck 60 F254. Column chromatography was done with
silica gel Merck 60 (0.063–0.2 mm). All reactions involving
air-sensitive agents were conducted under argon atmosphere
applying Schlenk-technique. All reagents purchased from
suppliers were used without further purification. CH2Cl2 was
dried and distilled over P2O5, toluene was dried by azeotropic
distillation, followed by distillation over sodium. Solvents for
chromatography were distilled prior to use.
2
2
(t, C-14), 33.3 (dt, JC,F = 16.5 Hz, C-3), 33.7 (dt, JC,F
=
1
21.6 Hz, C-1), 92.1 (dd, JC,F = 175.5 Hz, C-2). 19F NMR
(CDCl3) d À178.0 (m). GC/MS (70 eV): m/z (%) 324/
322 (0/0) [M+], 304/302 (1/1) [M+ À HF], 276/274 (1/1), 241
(1) [M+ À HBr À H], 189 (2) [M+ + H À HF À HBr], 163 (7),
111 (13) [C8H15+], 97 (57) [C7H13+], 85 (33) [C6H13+], 83
(55) [C6H11+], 71 (56) [C5H11+], 69 (45) [C5H9 ], 57 (100)
+
+
[C4H9 ], 55 (54) [C4H7 ], 43 (88) [C3H7 ], 41 (45) [C3H5 ].
+
+
+
4.3. Dehydrobromination of bromofluorides
4.3.1. 2-Fluorohex-1-ene (3a)
In a two-necked flask with a distillation bridge powdered
KOH (13.00 g, 232 mmol) was treated drop wise with the
mixture prepared in Section 4.2.1 (13.00 g, 63 mmol of 2a)
and heated to 95 8C until the formed vinyl fluoride 3a
distilled completely (4–48 h depending on the particle size
of KOH). Yield: 5.27 g (82%, based on the part of 2a
contained in the starting material). The spectroscopic data
agree with those published in Ref. [65].
4.2. General procedure for bromofluorination
A solution of 100 mmol of the corresponding terminal
1 and triethylamine trihydrofluoride (25 mL,
alkene
153 mmol) in CH2Cl2 (100 mL) under stirring at 0 8C
was treated in portions with NBS (21.9 g, 120 mmol). The
mixture was stirred overnight while warming up to room
temperature. The yellowish suspension was poured into ice
water (500 mL) and treated with a conc. ammonia solution
until the pH was significantly basic. The aqueous phase was
extracted with pentane (3 Â 150 mL). The combined organic
layer was washed with 2N HCl (2 Â 150 mL) and with 5%
NaHCO3-solution (3 Â 150 mL) and water (150 mL). After
removing of the solvent the residue can be purified by
column chromatography. Generally, the crude product was
used for the next step.
The corresponding bromofluoride 2 (50.0 mmol) in
pentane (500 mL) was refluxed with potassium tert-
butanolate (6.74 g, 60 mmol) for 5 h. The mixture was
poured into water (500 mL), the phases were separated and
the organic layer was washed with water (200 mL) and 5%
aqueous NaHCO3 solution (200 mL). After drying of the
organic phase over MgSO4, the solvent was removed and the
crude product was purified.
4.3.2. 2-Fluorodec-1-ene (3b)
The mixture from 4.2.2 (22.49 g, 94 mmol) was refluxed
with potassium tert-butanolate (12.63 g, 113 mmol) in
pentane (1200 mL) for 5 h. The mixture was poured into
water (1000 mL), the phases were separated and the organic
layer was washed with water (200 mL) and 5% aqueous
NaHCO3 solution (200 mL). After drying of the organic
phase over MgSO4, the solvent was removed and the crude
product was distilled. Yield: 9.58 g (65%, mixture of 85%
3b, 12% dec-1-yne, 3% of 1-fluorodecene, 69% yield of 3b
4.2.1. 1-Bromo-2-fluorohexane (2a)
According to the general procedure 2a was prepared from
1a (8.40 g, 0.1 mol). Yield: 17.65 g (96%) (contaminated
with 8% of the regioisomer and 4% of the 1,2-dibromide).
The spectroscopic data agree with those published in
Ref. [64].

F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
1599
based on 2b). b.p. 71 8C at 27 mbar (Lit.: 95 8C at 133 mbar
[48]). The spectroscopic data agree with those published in
Ref. [46].
4.4.1. 2-Fluorohex-1-en-3-ol (4a)
Compound 3a (9.30 g, 91 mmol) was reacted according
to the general procedure. Due to the volatility of the product
a different work-up was necessary. After completion of the
reaction the mixture was treated with pentane (300 mL) and
diethyl ether (90 mL). The organic phase was washed with
10% KOH (4 Â 80 mL) and with a sat. NaCl solution
(30 mL). After drying the solvent was evaporated and the
residue was distilled. Yield: 7.00 g (65%). b.p. 33–35 8C at
80 mbar. 1H NMR (CDCl3): d 0.95 (t, 3JH,H = 7.4 Hz, 3 H, 6-
CH3), 1.44 (m, 2 H, 5-CH2), 1.65 (m, 2 H, 4-CH2), 1.83 (br s,
4.3.3. 2-Fluorohexadec-1-ene (3c)
Similar to the above-mentioned procedure 3c was
prepared from pure 2c (16.12 g, 50 mmol). Yield: 12.50 g
(mixture of 72% 2c, 23% 1-bromohexadec-1-ene, 2%
hexadec-1-yne). 1H NMR (CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz,
3 H, 16-CH3), 1.26 (m, 22 H, 5-CH2–15-CH2), 1.50 (m, 2 H,
3
4-CH2), 2.17 (m, 2 H, 3-CH2), 4.17 (dd, JH,F = 50.3 Hz,
1 H, OH), 4.13 (ddd, 3JH,H = 5.7 Hz, 3JH,H = 7.2 Hz, 3JH,F
2
12.9 Hz, 1 H, 3-CH), 4.52 (dd, JH,H = 3.1 Hz, JH,F
=
=
=
2JH,H = 2.4 Hz, 1 H, 1-CH2), 4.47 (dd, 3JH,F = 17.4 Hz, 2JH,H
= 2.4 Hz, 1 H, 1-CH2). 13C NMR (CDCl3): d 14.1 (q, C-16),
22.7 (t, C-15), 26.0 (t, C-4), 28.9, 29.4, 29.5, 29.6, 29.7 (t, C-
5–C-13), 31.9 (dt, 2JC,F = 28.0 Hz, C-3), 31.9 (t, C-14), 89.1
(dt, 2JC,F = 21.6 Hz, C-1), 167.1 (d, 1JC,F = 256.9 Hz, C-2).
3
2
3
49.6 Hz, 1 H, 1-CH2), 4.65 (dd, JH,H = 3.1 Hz, JH,F
17.8 Hz, 1 H, 1-CH2). 13C NMR (CDCl3): d 13.7 (q, C-6),
18.4 (t, C-5), 36.1 (t, C-4), 70.1 (dd, 2JC,F = 30.5 Hz, C-3),
90.0 (dt, 2JC,F = 17.8 Hz, C-1), 166.9 (d, 1JC,F = 259.4, C-2).
3
3
19F NMR (CDCl3): d À95.0 (ddt, JH,F = 17.2 Hz, JH,F
=
19F NMR (CDCl3): d À111.8 (ddd, 3JH,F = 11.5 Hz, 3JH,F
=
3
17.2 Hz, JH,F = 51.5 Hz). GC/MS (70 eV): m/z (%) 242
(0.2) [M+], 222 (4) [M+ À HF], 180 (7) [M+ À HF À C3H6],
166 (6) [180 À CH2], 152 (7) [180 À C2H4], 152 (6) [180 À
C3H6], 138 (8) [180 À C4H8], 125 (11), 124 (9) [180 À
C5H10], 110 (22) [180 À C6H12], 96 (64) [180 À C7H14], 85
(16) [C6H13+], 82 (100) [180 À C8H16], 71 (35) [C5H11+], 69
17.2 Hz, 3JH,F = 49.6 Hz). GC/MS (70 eV): m/z (%) 118 (1)
[M+], 103 (2) [M+ À CH3], 90 (8) [M+ + H À C2H5], 76 (25)
[C3H5OF+], 75 (100) [C3H4OF+], 71 (14), 55 (11) [75 À
+
+
HF], 43 (58) [C3H7 ], 41 (47) [C3H5 ].
+
+
+
(84) [C5H9 ], 57 (88) [C4H9 ], 55 (81) [C4H7 ], 43 (100)
+
[C3H7 ], 41 (62) [C3H5 ].
+
4.4.2. 2-Fluorodec-1-en-3-ol (4b)
According to the general procedure 4b was prepared from
9.42 g (59.6 mmol) 3b. The product 4b was purified by
column chromatography with cyclohexane/ethyl acetate
(10:1). Yield: 4.87 g (47%). The spectroscopic data agree
with those published ones [48].
4.3.4. (E)-1-Fluorocyclododecene
Similar to the procedure mentioned above, (E)-1-
fluorocyclododecene (21) was prepared from diastereopure
cis-1-bromo-2-fluorocyclododecane (20) [43,44] (13.25 g,
50.0 mmol) by refluxing with KOtBu (11.23 g, 100 mmol) in
cyclohexane (650 mL) for 5 h. Yield: 9.02 g (98%). The
spectroscopic data agree with published ones [66].
4.4.3. 2-Fluorohexadec-1-en-3-ol (4c)
According to the general procedure 4c was prepared from
10.0 g (29.8 mmol) 3c. The product 4c was purified by
column chromatography with cyclohexane/ethyl acetate
(10:1). Yield: 4.25 g (55%). m.p. 30 8C (pentane). 1H NMR
(CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 16-CH3), 1.26 (m, 22
H, 5-CH2–15-CH2), 1.54–1.76 (m, 2 H, 4-CH2), 1.90 (br s, 1
4.4. General procedure for the allylic oxygenation of vinyl
fluorides with selenium dioxide
A solution of selenium dioxide (5.55 g, 50 mmol) and
80% tert-butyl hydroperoxide in di-tert-butyl ether (25 mL,
200 mmol) in CH2Cl2 (100 mL) was treated with the
corresponding fluorolefin 3 (20 mmol) and acetic acid
(2.3 mL, 40 mmol). Subsequently, the mixture was stirred
for 4–14 days at room temperature. Then toluene (10 mL)
was added to precipitate SeO2, which was separated. Then
CH2Cl2 was removed without heating in vacuo. The residue
was dissolved in diethyl ether (20 mL) and the solution was
washed with 10% aqueous KOH (4 Â 10 mL) in order to
separate remaining SeO2. To reduce the excess peroxide the
solution was stirred with 5 g of FeSO4Á7H2O at room
temperature for 4 h. The colored suspension was filtered and
the residue was washed with diethyl ether. The solution was
washed with 2N HCl (20 mL) and with a sat. NaCl solution
(30 mL). The solution was dried with MgSO4 and the
solvent was evaporated. The crude product was purified by
column chromatography.
H, OH), 4.10 (dddd, 4JH,H = 0.5 Hz, 3JH,H = 5.8 Hz, 3JH,H
=
=
3
7.6 Hz, JH,F = 13.1 Hz, 1 H, 3-CH), 4.52 (ddd, JH,H
4
3
2
0.5 Hz, JH,F = 49.4 Hz, JH,H = 3.1 Hz, 1 H, 1-CH2), 4.64
(dd, 3JH,F = 17.4 Hz, 2JH,H = 3.1 Hz, 1 H, 1-CH2). 13C NMR
(CDCl3): d 14.1 (q, C-16), 22.7 (t, C-15), 25.1 (t, C-5), 29.4,
29.5, 29.6, 29.7, 31.9, 34.0 (t, C-4 and C-6–C-14), 70.3 (dd,
2JC,F = 31.9 Hz, C-3), 90.0 (dd, 2JC,F = 18.0 Hz, C-1), 166.8
1
(d, JC,F = 260.8 Hz, C-2). 19F NMR (CDCl3): d À111.7
(ddd, 3JH,F = 13.4 Hz, 3JH,F = 17.2 Hz, 3JH,F = 49.6 Hz). GC/
MS (70 eV): m/z (%) 258 (1) [M+], 240 (1) [M+ À H2O], 211
(11) [240 À C2H5], 182 (2) [C13H26+ (McLafferty)], 166 (4),
137 (5), 114 (12), 113 (8) [C8H17+], 99 (9) [C7H15+], 97 (20)
[C7H13+], 86 (36), 85 (19) [C6H13+], 83 (25) [C6H11+], 76
(69) [C3H5OF+], 75 (75) [C3H4OF+], 71 (40) [C5H11+], 69
+
+
+
(36) [C5H9 ], 57 (88) [C4H9 ], 55 (50) [C4H7 ], 43 (100)
+
+
[C3H7 ], 41 (55) [C3H5 ]. Calcd. for C16H31FO (258.24): C
74.37, H 12.09. Found: C 74.76, H 12.53.

1600
F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
4.4.4. (Z)-2-Fluorocyclododec-2-en-1-ol (22)
clear solution was stirred overnight while warming to room
temperature. Then 2N HCl (150 mL) was added at room
temperature and stirring was continued for 4 h. The layers
were separated and the aqueous phase was extracted with
CH2Cl2 (2 Â 50 mL). The combined organic phases were
washed with 2N HCl (2 Â 100 mL) and a 5% NaHCO3-
solution (100 mL) and dried over MgSO4. The solvent was
removed in vacuo and the product was purified by column
chromatography (cyclohexane/ethyl acetate, 10:1). Yield:
720 mg (25%). 1H NMR (CDCl3): d 0.87 (t, 3JH,H = 6.7 Hz, 3
H, 10-CH3), 1.20–1.43 (m, 10 H, 5-CH2–9-CH2), 1.65 (s, 1
According to the general procedure 22 was prepared from
(E)-1-fluorocyclododec-1-en (21) (7.00 g, 38 mmol). After
50% conversion of 21 the crude product was purified by
column chromatography (cyclohexane/ethyl acetate, 10:1)
to give a 92:8 mixture of 22 and its (E)-isomer. Yield: 1.96 g
(27%). 1H NMR (CDCl3): d 1.08–1.62 (m, 14 H, 5-CH2–11-
CH2), 1.65–1.82 (m, 2 H, 12-CH2), 1.90–2.10 and 2.30–2.43
=
3
(m, 2 H, 4-CH2), 2.16 (s, 1 H, OH), 4.10 (ddd, JH,H
3
3
4.5 Hz, JH,H = 9.5 Hz, JH,F = 21.7 Hz, 1 H, 1-CH), 4.84
(ddd, 3JH,H = 6.2 Hz, 3JH,H = 9.5 Hz, 3JH,F = 37.2 Hz, 1 H, 3-
3
3
3
CH). 13C NMR (CDCl3): d 22.2 (dt, JC,F = 3.8 Hz, C-4),
22.9, 24.0, 24.7, 25.4, 25.7, 25.8 (t, C-5–C-11), 31.9 (t, C-
H, OH), 2.10 (dt, JH,H = 6.9 Hz, JH,H = 6.9 Hz, 2 H, 4-
CH2), 4.10 (d, 3JH,F = 15.7 Hz, 2 H, 1-CH2), 4.83 (dt, 3JH,H
=
2
2
3
12), 71.7 (dd, JC,F = 30.5 Hz, C-1), 108.8 (dd, JC,F
=
7.5 Hz, JH,F = 37.2 Hz, 1 H, 3-CH). 13C NMR (CDCl3): d
14.0 (q, C-10), 22.6 (t, C-4), 23.3 (t, C-9), 29.0–29.1 (3 t, C-
5–C-7), 31.7 (t, C-8), 61.4 (dt, 2JC,F = 30.5 Hz, C-1), 108.1
(dd, 2JC,F = 12.7 Hz, C-3), 157.5 (d, 1JC,F = 254.3 Hz, C-2).
1
14.0 Hz, C-3), 158.2 (d, JC,F = 255.6 Hz, C-2). 19F NMR
(CDCl3): d À129.3 (m). GC/MS (70 eV): m/z (%) 201 (2)
[M+ + H], 200 (3) [M+], 183 (1) [M+ + H À H2O], 180 (5)
[M+ À HF], 161 (2), 139 (5), 125 (8), 111 (13), 98 (16), 88
(100), 81 (23), 67 (28), 55 (30), 41 (39).
3
3
19F NMR (CDCl3): d À121.8 (dt, JH,F = 34.3 Hz, JH,F
=
17.2 Hz). GC/MS (70 eV): m/z (%) 175 (2) [M + H+], 174 (9)
[M+], 156 (3) [M+ À H2O], 154 (0) [M+ À HF], 139 (0.5)
[154 À CH3], 123 (30) [154 À CH2OH], 113 (10) [C8H17+],
4.4.5. 1-Fluoro-1-octyloxirane (5)
99 (15) [C7H15+], 85 (14) [M+ À C4H6OF], 84 (14) [C6H12
+
A solution of 2-fluorodec-1-ene (3b) (5.64 g, 30.3 mmol
3b, containing 15% dec-1-yne) in CH2Cl2 (100 mL) was
stirred with meta-chloroperbenzoic acid (7.80 g, 29.8 mmol,
75% purity) at room temperature for 48 h, while the clear
solution became muddy and meta-chlorobenzoic acid
precipitated as a white solid. After filtration the colorless
solution was extracted with a 0.1N Na2S2O3-solution
(50 mL) and a sat. NaHCO3 solution (50 mL). After drying
over MgSO4 and evaporation of the solvent, the residue was
distilled over a Vigreux column at 1.2–1.5 mbar. A fraction
distilling between 45 and 65 8C was collected and analysed.
Yield: 4.38 g (66% of compound 5, 17% of starting material
3b and 17% of dec-1-yne). 1H NMR (CDCl3): d 0.88 (t, 3JH,H
(McLafferty)], 81 (46), 70 (47) [C4H6O+], 69 (67) [C5H9 ],
+
+
57 (53) [C4H9 ], 56 (69), 55 (68) [C4H7 ], 43 (100) [C3H7 ],
+
+
+
41 (84) [C3H5 ].
4.5. General procedure for the synthesis of acetates and
chloroacetates (method A)
The corresponding allylic alcohol 4 (5 mmol) was
dissolved in dry CH2Cl2 (5 mL) and treated with pyridine
(0.44 g, 5.57 mmol). Then acetic anhydride (0.58 g,
5.5 mmol) or solid chloroacetic anhydride (0.94 g, 5.5 mmol)
was dissolved under stirring and a catalytic amount of DMAP
was added. After stirring overnight at room temperature the
reaction mixture was dissolved in diethyl ether (30 mL) and
washed with 2N aq. HCl (15 mL), a 5% NaHCO3-solution
(20 mL) and brine. The organic layer was dried over MgSO4
and the solvent was removed. The product was purified by
column chromatography.
= 6.9 Hz, 3 H, 10-CH3), 1.28 (m, 10 H, 5-CH2–9-CH2), 1.52
2
(m, 2 H, 4-CH2), 1.97 (m, 2 H, 3-CH2), 2.66 (dd, JH,H
=
=
3
2
4.3 Hz, JH,F = 1.2 Hz, 1 H, 1-CH2), 3.06 (dddd, JH,H
4.3 Hz, 3JH,F = 1.2 Hz, 4JH,H = 1.7 Hz, 4JH,H = 0.5 Hz, 1 H,
1-CH2). 13C NMR (CDCl3): d 14.0 (q, C-10), 22.6 (t, C-4),
23.5 (t, C-9), 29.1, 29.2, 29.3 (t, C-5–C-7), 31.8 (t, C-8), 31.8
2
2
(dt, JC,F = 30.5 Hz, C-3), 50.8 (dt, JC,F = 22.9 Hz, C-1),
95.2 (d, 1JC,F = 261.9 Hz, C-2). 19F NMR (CDCl3): d À134.8
(ps t, 3JH,F = 15.3 Hz). GC/MS (70 eV): m/z (%) 174 (0.07)
[M+], 145 (6) [M+ À C2H5], 131 (10) [M+ À C3H7], 123 (15),
103 (13) [M+ À C5H11], 98 (20) [C7H14+], 89 (100) [M+ À
4.5.1. 3-Acetoxy-2-fluorodec-1-ene (9b)
According to the general procedure 2-fluorohex-1-en-3-
ol (4b) (174 mg, 1.0 mmol) was acetylated to give the ester
9b. Yield: 210 mg (91%). 1H NMR (CDCl3): d 0.88 (t, 3JH,H
= 6.9 Hz, 3 H, 10-CH3), 1.21–1.39 (m, 10 H, 5-CH2–9-CH2),
1.72 (m, 2 H, 4-CH2), 2.08 (s, 3 H, 12-CH3), 4.53 (dd, 2JH,H
C6H13], 81 (29), 76 (50) [C3H5OF+], 55 (67) [C4H7 ], 43
+
+
(47) [C3H7 ], 41 (75) [C3H5 ].
+
3
2
= 3.1 Hz, JH,F = 48.6 Hz, 1 H, 1-CH2), 4.70 (dd, JH,H
3
=
=
3
4.4.6. 2-Fluorodec-2-en-1-ol (6)
3.1 Hz, JH,F = 16.7 Hz, 1 H, 1-CH2), 5.28 (dt, JH,H
3
In a dried Schlenk vessel the crude epoxide prepared
above (4.38 g, containing 22.5 mmol of 5) was dissolved in
CH2Cl2 (10 mL) under argon. To this solution under stirring
trimethylsilyl triflate (TMSOTf) (5.55 g, 25.0 mmol) in dry
CH2Cl2 (20 mL) was dropped at 0 8C within 10 min. Then
triethylamine (2.53 g, 25.0 mmol) was dropped to the red
brown mixture at the same temperature within 30 min. The
6.9 Hz, JH,F = 16.2 Hz, 1 H, 3-CH). 13C NMR (CDCl3): d
13.9 (q, C-10), 20.8 (q, C-12), 22.5 (t, C-9), 24.9 (t, C-5),
29.0 (t, C-4), 29.1 (t, C-7), 31.0 (t, C-6), 31.7 (t, C-8), 71.3
2
2
(dd, JC,F = 30.5 Hz, C-3), 92.4 (dt, JC,F = 28.7 Hz, C-1),
1
163.0 (d, JC,F = 261.9 Hz, C-2), 169.8 Hz (s, C-11). 19F
3
3
NMR (CDCl3): d À111.5 (ddd, JH,F = 47.7 Hz, JH,F
=
17.2 Hz, 3JH,F = 15.2 Hz). GC/MS (70 eV): m/z (%) 216 (0)

F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
1601
[M+], 174 (7) [M+ + H À CH3CO], 156 (1) [M+
À
(dt, 3JC,F = 3.8 Hz, C-4), 30.9 (t, C-6), 31.9 (t, C-14), 40.7 (t,
2
C-18), 73.4 (dd, JC,F = 30.5 Hz, C-3), 93.4 (dd, JC,F =
2
CH3COOH (McLafferty)], 141 (1) [156 À CH3], 127 (6),
118 (2) [C5H7O2F+ (McLafferty)], 113 (3), 99 (4) [156 À
17.8 Hz, C-1), 161.8 (d, 1JC,F = 260.7 Hz, C-2), 166.3 (s, C-
17). 19F NMR (CDCl3): d À112.0 (d ps t, JH,F = 17.2 Hz,
+
+
C4H9], 69 (5) [C5H9 ], 57 (8) [C4H9 ], 55 (15) [C4H7 ], 43
+
3
3JH,F = 47.7 Hz). GC/MS (70 eV): m/z (%) 334 (0.1) [M+],
317 (0.2) [M+ À OH], 314 (0.3) [M+ À HF], 299 (5) [M+ À
Cl], 285 (3) [M+ À CH2Cl], 258 (22) [M+ + H À
CH2ClCOO], 240 (5) [M+ À HO2CH2Cl], 211 (23), 180 (8),
152 (17) [M+ + H À C13H27], 95 (47), 86 (100), 70 (65), 57
+
(100) [CH3CO], 41 (21) [C3H5 ].
4.5.2. 3-Chloroacetoxy-2-fluorohex-1-ene (10a)
According to the general procedure the 2-fluorohex-1-en-
3-ol (4a) (590 mg, 5.0 mmol) was esterified. Yield: 770 mg
(79%). 1H NMR (CDCl3): d 0.95 (t, 3JH,H = 7.4 Hz, 3 H, 6-
CH3), 1.39 (m, 2 H, 5-CH2), 1.77 (m, 2 H, 4-CH2), 4.08 (s, 2
H, 8-CH2), 4.61 (dd, 2JH,H = 3.3 Hz, 3JH,F = 47.9 Hz, 1 H, 1-
CH2), 4.77 (dd, 2JH,H = 3.3 Hz, 3JH,F = 16.5 Hz, 1 H, 1-CH2),
+
+
+
(83) [C4H9 ], 55 (84) [C4H7 ], 43 (100) [C3H7 ].
4.5.5. 3-Chloroacetoxy-2-fluoropropene (10d)
According to the general procedure 2-fluoroprop-2-enol
(4d) (760 mg, 10.0 mmol) was esterified to give 6d. Yield:
1.28 g (84%). 1H NMR (CDCl3): d 4.12 (s, 2 H, 5-CH2Cl),
4.68 (dd, 2JH,H = 3.3 Hz, 3JH,F = 46.7 Hz, 1 H, 3-CH2), 4.71
3
3
5.36 (dt, JH,H = 6.9 Hz, JH,F = 16.5 Hz, 1 H, 3-CH). 13C
NMR (CDCl3): d 13.5 (q, C-6), 18.1 (t, C-5), 32.9 (t, C-4),
40.7 (t, C-8), 73.1 (dd, 2JC,F = 28.0 Hz, C-3), 93.5 (dt, 2JC,F
=
17.8 Hz, C-1), 161.8 (d, 1JC,F = 261.9 Hz, C-2), 166.4 (s, C-
7). 19F NMR (CDCl3): d À112.1 (ps dt, 3JH,F = 16.2 Hz, 3JH,F
= 47.7 Hz). GC/MS (70 eV): m/z (%) 195 (1) [M+ + H], 179
(1) [M+ À CH3], 167/165 (2/9) [M+ À C2H5], 154/152 (6/15)
[M+ À C3H6], 118 (46) [C6H11OF+ (McLafferty)], 100 (100)
[118 À H2O], 85 (55) [100 À CH3], 79/77 (28/100)
[C2H2OCl+], 72 (16), 59 (18), 51/49 (6/21) [CH2Cl+], 41
(d, JH,F = 14.7 Hz, 2 H, 1-CH2), 4.86 (dd, JH,H = 3.3 Hz,
3JH,F = 15.5 Hz, 1 H, 3-CH2). 13C NMR (CDCl3): d 40.4 (t,
3
2
2
2
C-5), 62.6 (dt, JC,F = 33.1 Hz, C-1), 95.2 (dt, JC,F
=
16.5 Hz, C-3), 159.3 (d, 1JC,F = 258.1 Hz, C-2), 166.6 (s, C-
4). 19F NMR (CDCl3): d À106.1 (ddt, 3JH,F = 15.3 Hz, 3JH,F
= 15.3 Hz, 3JH,F = 47.7 Hz). GC/MS (70 eV): m/z (%) 154/
152 (0.5/1) [M+], 134/132 (0/1) [M+ À HF], 117 (1) [132 À
CH3], 97 (2), 76 (94) [C3H4OF+], 59 (100) [C3H4F+], 51/49
(16/49) [CH2Cl+], 42 (27).
+
(19) [C3H5 ].
4.5.3. 3-Chloroacetoxy-2-fluorodec-1-ene (10b)
According to the general procedure the 2-fluorodec-1-en-
3-ol (4b) (870 mg, 5.0 mmol) was esterified to give 10b.
=
6.9 Hz, 3 H, 10-CH3), 1.28 (m, 10 H, 5-CH2–9-CH2), 1.77
4.5.6. 1-Chloroacetoxy-2-fluorodec-2-ene (12)
According to the general procedure the fluoroallylic
alcohol 6 (174 mg, 1.0 mmol) was esterified. Yield: 248 mg
(99%). 1H NMR (CDCl3): d 0.88 (t, 3JH,H = 6.7 Hz, 3 H, 10-
CH3), 1.28 (m, 10 H, 5-CH2–9-CH2), 2.12 (m, 2 H, 4-CH2),
4.09 (s, 2 H, 12-CH2), 4.67 (d, 3JH,F = 17.9 Hz, 2 H, 1-CH2),
1
Yield: 1.14 g (92%). H NMR (CDCl3): d 0.88 (t, JH,H
3
2
(m, 2 H, 4-CH2), 4.07 (s, 2 H, 12-CH2), 4.60 (dd, JH,H
=
=
=
3
3.3 Hz, JH,F = 47.9 Hz, 1 H, 1-CH2), 4.76 (dd, JH,H
2
3
3.3 Hz, JH,F = 16.5 Hz, 1 H, 1-CH2), 5.34 (dt, JH,H
3
3
3
4.98 (dt, JH,H = 7.6 Hz, JH,F = 35.3 Hz, 1 H, 3-CH). 13C
NMR (CDCl3): d 14.0 (q, C-10), 22.6 (t, C-9), 23.6 (dt, 3JC,F
= 3.8 Hz, C-4), 28.8, 29.0, 29.0 (t, C-5–C-7), 31.7 (t, C-8),
3
6.9 Hz, JH,F = 16.5 Hz, 1 H, 3-CH). 13C NMR (CDCl3): d
3
14.0 (q, C-10), 22.5 (t, C-9), 24.8 (t, C-5), 29.0 (dt, JC,F
=
5.1 Hz, C-4), 29.2 (t, C-7), 30.8 (t, C-6), 31.6 (t, C-8), 40.7 (t,
2
40.6 (t, C-12), 63.8 (dt, JC,F = 31.8 Hz, C-1), 113.0 (dd,
2
C-12), 73.4 (dd, JC,F = 30.5 Hz, C-3), 93.4 (dt, JC,F
2
=
2JC,F = 12.7 Hz, C-3), 152.6 (d, 1JC,F = 253.0 Hz, C-2), 166.8
(s, C-11). 19F NMR (CDCl3): d À119.8 (dt, 3JH,F = 19.1 Hz,
3JH,F = 36.2 Hz). GC/MS (70 eV): m/z (%) 252/250 (0/0)
[M+], 216 (1) [M+ + H À Cl], 215 (4) [M+ À Cl], 201 (3) [M+
À CH2Cl], 174 (4) [M+ + H À C2H2O2Cl], 167/165 (62/57)
[M+ À C6H13], 156 (5) [M+ À C2H3O2Cl], 136 (2) [156 À
HF], 127 (9), 113 (13) [C8H17+], 99 (23) [C7H13+], 96 (24),
86 (35) [M+ À C4H4O2FCl], 77 (56) [C2H2OCl], 72 (46), 57
17.8 Hz, C-1), 161.8 (d, 1JC,F = 259.5, C-2), 166.3 (s, C-11).
19F NMR (CDCl3): d À112.1 (ps dt, 3JH,H = 15.3 Hz, 3JH,H
=
49.6 Hz). GC/MS (70 eV): m/z (%) 250 (0) [M+], 215 (4)
[M+ À Cl], 201 (5) [M+ À CH2Cl], 174 (57) [M+ + H À
C2H2OCl], 152 (24) [M+ + H À C7H15], 127 (31), 113 (27)
[127 À CH2], 99 (41) [127 À C2H4], 86 (54), 77 (100)
[C2H2OCl+], 57 (33) [C4H9 ], 55 (51) [C4H7 ], 43 (57)
+
+
+
[C3H7 ], 41 (35) [C3H5 ].
+
+
+
+
(21) [C4H9 ], 56 (441), 55 (51) [C4H7 ], 43 (100) [C3H7 ],
+
41 (54) [C3H5 ].
4.5.4. 3-Chloroacetoxy-2-fluorohexadec-1-ene (10c)
According to the general procedure 2-fluorohexadec-1-
en-3-ol (4c) (1.032 g, 4.0 mmol) was esterified. Yield:
1.26 g (95%). 1H NMR (CDCl3): d 0.88 (t, 3JH,H = 6.4 Hz, 3
H, 16-CH3), 1.31 (m, 22 H, 5-CH2–15-CH2), 1.77 (m, 2 H, 4-
4.5.7. (Z)-3-Chloroacetoxy-2-fluorocyclododecene (23)
According to the general procedure the fluoroallylic
alcohol 22 (400 mg, 2.0 mmol) was esterified to give the
ester (Z)-23 after chromatography (silica gel, cyclohexane/
ethyl acetate, 40:1). Yield: 0.35 g (63%). 1H NMR (CDCl3):
d 1.17–1.69 (m, 14 H, 5-CH2–11-CH2), 1.73–1.90 (m, 2 H,
4-CH2), 1.93–2.07 (m, 1 H, 12-CH2), 2.33–2.48 (m, 1 H, 12-
CH2), 4.05 (s, 2 H, 14-CH2), 5.01 (ddd, 3JH,H = 5.7 Hz, 3JH,H
CH2), 4.07 (s, 2 H, 18-CH2), 4.60 (dd, 2JH,H = 3.2 Hz, 3JH,F
=
=
=
2
47.9 Hz, 1 H, 1-CH2), 4.76 (dd, JH,H = 3.2 Hz, JH,F
3
3
16.5 Hz, 1 H, 1-CH2), 5.33 (dt, JH,H = 6.9 Hz, JH,F
3
16.5 Hz, 1 H, 3-CH). 13C NMR (CDCl3): d 14.0 (q, C-16),
22.6 (t, C-15), 24.8 (t, C-5), 29.1–29.6 (t, C-7–C-13), 29.6
3
3
= 10.3 Hz, JH,F = 36.2 Hz, 1 H, 3-CH), 5.28 (ddd, JH,H
=

1602
F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
3
3
5.2 Hz, JH,H = 10.0 Hz, JH,F = 23.8 Hz, 1 H, 1-CH). 13C
(dd, 2JH,H = 3.1 Hz, 3JH,F = 16.7 Hz, 1 H, 1-CH2), 5.28 (dt,
3
NMR (CDCl3): d 22.7 (dt, JC,F = 3.8 Hz, C-4), 23.1, 24.1,
3
3JH,H = 6.7 Hz, JH,F = 16.0 Hz, 1 H, 3-CH). 13C NMR
(CDCl3): d 9.0 (q, C-13), 14.0 (q, C-10), 22.6 (t, C-9), 24.9 (t,
24.3, 24.5, 25.5, 25.7, 26.1, 28.5 (t, C-5–C-12), 40.9 (t, C-
2
14), 75.3 (dd, JC,F = 29.3 Hz, C-1), 112.9 (dd, JC,F
14.0 Hz, C-3), 154.0 (d, 1JC,F = 255.6 Hz, C-2), 166.3 (s, C-
13). 19F NMR (CDCl3): d À128.6 (dd, 3JH,F = 22.9 Hz, 3JH,F
= 36.2 Hz).
2
=
C-5), 27.6 (t, C-12), 29.0 (t, C-4), 29.1 (t, C-7), 31.1 (t, C-6),
31.7 (t, C-8), 71.2 (dd, 2JC,F = 30.5 Hz, C-3), 92.3 (dt, 2JC,F
=
17.8 Hz, C-1), 162.9 (d, 1JC,F = 259.4 Hz, C-2), 173.3 (s, C-
3
11). 19F NMR (CDCl3): d À111.5 (ddd, JH,F = 15.3 Hz,
3JH,F = 17.2 Hz, 3JH,F = 49.6 Hz). GC/MS (70 eV): m/z (%)
4.6. General procedure for synthesis of propionates
(method B)
230 (0) [M+], 174 (14) [M+ À C3H4O], 156 (2) [M+
À
C3H6O2], 145 (4) [M+ À C6H13], 127 (6), 113 (3) [C8H17+],
86 (10), 57 (100) [C3H5O+] and [C4H9 ], 55 (18) [C4H7 ], 43
+
+
+
(17) [C3H7 ], 41 (23) [C3H5 ].
+
The corresponding fluorinated allylic alcohol
4
(10 mmol) in CH2Cl2 (40 mL) under stirring was treated
with dicyclohexylcarbodiimide (DCC) (2.28 g, 11.0 mmol)
and subsequently with propionic acid (814 mg, 11.0 mmol).
Then a catalytic amount of N,N-dimethylaminopyridine
(DMAP) was added and the mixture was stirred at room
temperature overnight. The reaction mixture was treated
with diethyl ether (200 mL), the dicyclohexyl urea was
filtered and the organic layer was washed with water (3 Â
40 mL), 5% aq. acetic acid (3 Â 40 mL) and again with
water (3 Â 40 mL). The organic layer was dried over
MgSO4, the solvent was removed and the residue was
purified by distillation or column chromatography.
4.6.3. 2-Fluoro-3-propionoxyhexadec-1-ene (11c)
According to the general procedure 4c (1.032 g,
4.00 mmol) and propionic acid (407 mg 5.5 mmol) were
reacted. The crude product was filtered through a 10 cm
column (silica gel, cyclohexane/ethyl acetate, 10:1) to give
1
11c as a colorless liquid. Yield: 931 mg (74%). H NMR
(CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 16-CH3), 1.16 (t, 3JH,H
= 7.6 Hz, 3 H, 19-CH3), 1.26 (m, 22 H, 5-CH2–15-CH2), 1.73
(m, 2 H, 4-CH2), 2.36 (q, 3JH,H = 7.6 Hz, 2 H, 18-CH2), 4.52
(dd, 2JH,H = 3.1 Hz, 3JH,F = 48.4 Hz, 1 H, 1-CH2), 4.70 (dd,
2JH,H = 3.1 Hz, 3JH,F = 16.7 Hz, 1 H, 1-CH2), 5.28 (dt, 3JH,H
=
6.9 Hz, 3JH,F = 16.0 Hz, 1 H, 3-CH). 13C NMR (CDCl3): d 9.0
(q, C-19); 14.0 (q, C-16), 22.7 (t, C-15), 24.9 (t, C-5), 27.6 (t,
C-18), 29.2, 29.3, 29.4, 29.5, 29.6, 29.6, 31.5, 31.9 (t, C-4 and
4.6.1. 2-Fluoro-3-propionoxyhexene (11a)
According to the general procedure 4a (590 mg,
5.00 mmol) and propionic acid (407 mg, 5.5. mmol) were
reacted. The crude product was filtered through a 10 cm
column (silica gel, n-pentane) to give 11a as a colorless
C-6–C-14), 71.2 (dd, 2JC,F = 31.8 Hz, C-3), 92.3 (dd, 2JC,F
=
17.8 Hz, C-1), 163.0 (d, 1JC,F = 260.7 Hz, C-2), 173.3 (s, C-
17). 19F NMR (CDCl3): d À111.4 (ddd, 3JH,F = 17.2 Hz, 3JH,F
3
1
= 15.3 Hz, JH,F = 47.7 Hz). GC/MS (70 eV): m/z (%) 314
liquid. Yield: 590 mg (68%). H NMR (CDCl3): d 0.94 (t,
3JH,H = 7.4 Hz, 3 H, 6-CH3), 1.16 (t, 3JH,H = 7.6 Hz, 3 H, 9-
CH3), 1.38 (m, 2 H, 5-CH2), 1.73 (m, 2 H, 4-CH2), 2.36 (q,
(0.4) [M+], 313 (0.4) [M+ À H], 299 (0.5) [M+ À CH3], 285
(14)[M+ À C2H5], 271(0.8)[M+ À C3H7], 258(33)[M+ +H À
C3H5O], 229 (3), 211 (16), 180 (5), 173 (4), [M+ À C10H21],
146 (15), 109 (11), 86 (44), 57 (100) [C3H5O+], 43 (41)
3JH,H = 7.6 Hz, 2 H, 8-CH2), 4.53 (dd, 2JH,H = 3.1 Hz, 3JH,F
=
=
=
2
48.4 Hz, 1 H, 1-CH2), 4.70 (dd, JH,H = 3.1 Hz, JH,F
3
+
3
3
[C3H7 ].
16.7 Hz, 1 H, 1-CH2), 5.30 (dt, JH,H = 6.9 Hz, JH,F
15.7 Hz, 1 H, 3-CH). 13C NMR (CDCl3): d 9.0 (q, C-9), 13.6
(q, C-6), 18.2 (t, C-5), 27.6 (t, C-8), 33.2 (t, C-4), 70.9 (dd,
2JC,F = 34.3 Hz, C-3), 92.3 (dt, 2JC,F = 17.8 Hz, C-1), 162.9
4.6.4. 2-Fluoro-3-propionoxypropene (11d)
According to the general procedure 4d (760 mg,
10.0 mmol) and propionic acid (814 mg, 11.0 mmol) were
reacted to give 11d after careful removing of the solvent using
a Vigreux column and bulp-to-bulp distillation of the residue.
1
(d, JC,F = 260.7 Hz, C-2), 173.3 (s, C-7). 19F NMR
3
3
(CDCl3):d À111.5 (ddd, JH,F = 15.3 Hz, JH,F = 17.2 Hz,
3JH,F = 47.7 Hz). GC/MS (70 eV): m/z (%) 174 (3) [M+], 145
(11) [M+ À C2H6], 132 (8), 118 (24) [C6H11OF+
(McLafferty)], 100 (38) [118 À H2O], 85 (27) [100 À
1
3
Yield: 700 mg (50%). H NMR (CDCl3): d 1.17 (t, JH,H
=
7.6 Hz, 3H, 6-CH3), 2.39(q, 3JH,H =7.6 Hz, 2 H, 5-CH2), 4.60
3
2
CH3], 73 (8) [C3H5O2 ], 57 (100) [C3H5O+], 41 (7) [C3H7 ].
+
+
(d, JH,F = 14.1 Hz, 2 H, 1-CH2), 4.61 (dd, JH,H = 3.3 Hz,
3JH,F = 47.5 Hz, 1 H, 3-CH2), 4.79 (dd, 2JH,H = 3.3 Hz, 3JH,F
16.9 Hz, 1 H, 3-CH2). 13C NMR (CDCl3): d 8.9 (q, C-6), 27.3
=
4.6.2. 2-Fluoro-3-propionoxydecene (11b)
2
2
(t, C-5), 61.1 (dt, JC,F = 35.6 Hz, C-1), 94.0 (dt, JC,F
=
According to the general procedure 4b (1.74 g,
10.0 mmol) and propionic acid (814 mg, 11.0 mmol) were
reacted. The crude product was filtered through a 10 cm
column (silica gel, cyclohexane/ethyl acetate, 10:1) to give
17.8 Hz, C-3), 160.5 (d, 1JC,F = 256.9 Hz, C-2), 173.6(s, C-4).
3
3
19F NMR (CDCl3): d À105.9 (ddt, JH,F = 15.3 Hz, JH,F
=
15.4 Hz, 3JH,F = 45.8 Hz). GC/MS (70 eV): m/z (%) 132 (1)
[M+], 75 (3) (C3H4OF+], 57 (100) [C3H5O+], 39 (4).
1
11b as a colorless liquid. Yield: 2.06 g (90%). H NMR
3
(CDCl3): d 0.89 (t, JH,H = 6.9 Hz, 3 H, 10-CH3), 1.15 (t,
3JH,H = 7.6 Hz, 3 H, 13-CH3), 1.29 (m, 10 H, 5-CH2–9-CH2),
1.73 (m, 2 H, 4-CH2), 2.35 (q, 3JH,H = 7.6 Hz, 2 H, 12-CH2),
4.52 (dd, 2JH,H = 3.1 Hz, 3JH,F = 48.4 Hz, 1 H, 1-CH2), 4.69
4.6.5. (Z)-2-Fluoro-1-propionoxydec-2-ene (13)
According to the general procedure 6 (174 mg,
1.00 mmol) was reacted with propionic acid (82 mg

F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
1603
1.10 mmol). After chromatographic purification (10 cm
silica gel, cyclohexane/ethyl acetate, 10:1) the product 13
(m, 4 H, 2-CH2 and 3-CH2), 3.68 (s, 3 H, 9-CH3), 4.54 (dt,
3
3JH,H = 7.4 Hz, JH,F = 45.3 Hz, 1 H, 5-CH). 13C NMR
1
was isolated as a colorless oil. Yield: 216 mg (94%). H
3
(CDCl3): d 13.4 (q, C-8), 22.5 (t, C-7), 25.4 (dt, JC,F
=
5.1 Hz, C-6), 27.6 (dt, JC,F = 29.2 Hz, C-3), 31.2 (t, C-2),
NMR (CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 10-CH3), 1.15
2
3
(t, JH,H = 7.6 Hz, 3 H, 13-CH3), 1.28 (m, 10 H, 5-CH2–9-
2
51.5 (q, C-9), 105.8 (dd, JC,F = 15.3 Hz, C-5), 157.7 (d,
CH2), 2.11 (m, 2 H, 4-CH2), 2.37 (q, 3JH,H = 7.6 Hz, 2 H, 12-
1JC,F = 251.8 Hz, C-4), 172.8 (s, C-1). 19F NMR (CDCl3): d
À112.0 (m). GC/MS (70 eV): m/z (%) 175 (3) [M+ + H], 174
(21) [M+], 154 (18) [M+ À HF], 143 (23) [M+ À CH3O], 132
(10) [M+ + H À C3H7], 111 (9), 101 (59) [M+ À C3H5O2], 97
CH2), 4.56 (d, 3JH,F = 17.9 Hz, 2 H, 1-CH2), 4.91 (dt, 3JH,H
=
3
7.6 Hz, JH,F = 35.8 Hz, 1 H, 3-CH). 13C NMR (CDCl3): d
8.9 (q, C-13), 14.0 (q, C-10), 22.6 (t, C-9), 23.5 (dt, 3JC,F
=
+
+
4.0 Hz, C-4), 27.4 (t, C-12), 28.9, 29.0, 29.0 (t, C-5–C-7),
31.7 (t, C-8), 62.2 (dt, 2JC,F = 31.8 Hz, C-1), 111.6 (dd, 2JC,F
= 14.0 Hz, C-3), 152.7 (d, 1JC,F = 253.0 Hz, C-2), 173.8 (s,
(62), 85 (73), 74 (100), [C3H6O2 ], 59 (31) [C2H3O2 ], 55
+
(13), 43 (19) [C3H7 ], 41 (14) [C3H5 ].
+
3
C-11). 19F NMR (CDCl3): d À119.5 (dt, JH,F = 19.1 Hz,
4.7.2. Methyl (Z)-4-fluorododec-4-enecarboxylate (7b)
According to the general procedure, from allylic alcohol
4b (174 mg, 1.00 mmol) the ester 7b was formed. Yield:
194 mg (84%). 1H NMR (CDCl3): d 0.80 (t, 3JH,H = 6.6 Hz, 3
H, 12-CH3), 1.23 (m, 10 H, 7-CH2–11-CH2), 1.96 (m, 2 H, 6-
CH2), 2.40 (m, 4 H, 2-CH2 and 3-CH2), 3.61 (s, 3 H, 13-
CH3), 4.46 (dt, 3JH,H = 7.4 Hz, 3JH,F = 37.7 Hz, 1 H, 5-CH).
13C NMR (CDCl3): d 13.9 (q, C-12), 22.5 (t, C-11), 23.4 (dt,
3JC,F = 5.1 Hz, C-6), 27.3 (t, C-2), 29.0, 31.1, 31.8 (t, C-7–C-
10), 29.2 (dt, 2JC,F = 28.0 Hz, C-3), 51.5 (q, C-13), 106.0 (dd,
2JC,F = 15.3 Hz, C-5), 157.6 (d, 1JC,F = 251.8 Hz, C-4), 172.6
(s, C-1). 19F NMR (CDCl3): d À112.1 (m). GC/MS (70 eV):
m/z (%): 230 (10) [M+], 211 (4) [M+ À F], 210 (28) [M+ À
HF], 199 (3) [M+ À OCH3], 178 (20) [210 À CH4O], 150
(20) [178 À CO], 145 (30), 136 (51) [M+ À HF À C3H6O2],
3JH,F = 36.2 Hz). GC/MS (70 eV): m/z (%) 230 (1) [M+], 201
(2) [M+ À C2H9], 187 (1) [M+ À C3H7], 174 (6) [M+ + H À
C3H5O2], 156 (7) [174 À H2O], 145 (11), 127 (3), 113 (5)
[C8H17+], 99 (9) [C7H15+], 86 (11), 72 (17), 67 (8), 57 (100)
+
+
[C3H5O], 43 (17) [C3H7 ], 41 (16) [C3H5 ].
4.6.6. (Z)-2-Fluoro-3-propionoxycyclododec-2-ene (24)
According to the general procedure the allylic alcohol 22
(202 mg, 1.00 mmol) was esterified. After chromatographic
purification (silica gel, cyclohexane/ethyl acetate, 10:1) the
ester 24 was isolated as a viscous oil. Yield: 210 mg (82%).
1H NMR (CDCl3): d 1.15 (t, 3JH,H = 7.4 Hz, 15-CH3), 1.17–
1.69 (m, 14 H, 5-CH2–11-CH2), 1.73–1.90 (m, 2 H, 4-CH2),
1.93–2.07 (m, 1 H, 12-CH2), 2.33 (q, 3JH,H = 7.4 Hz, 2 H, 14-
3
CH2), 2.33–2.48 (m, 1 H, 12-CH2), 4.95 (ddd, JH,H
+
=
5.7 Hz, JH,H = 10.0 Hz, JH,F = 36.5 Hz, 1 H, 3-CH), 5.23
97 (45) [C7H15+], 85 (53) [C6H13+], 74 (100) [C3H6O2
3
3
+
(McLafferty)], 59 (21) [CO2CH3 ], 57 (11) [C4H9 ], 55 (22)
+
(ddd, 3JH,H = 5.2 Hz, 3JH,H = 9.8 Hz, 3JH,F = 23.8 Hz, 1 H, 1-
[C4H7 ], 43 (36) [C3H7 ], 41 [C3H5 ].
+
+
+
3
CH). 13C NMR (CDCl3): d 9.0 (q, C-15), 22.6 (dt, JC,F
=
3.8 Hz, C-4), 23.1, 24.2, 24.4, 24.5, 25.5, 25.8, 26.1, 27.7,
4.7.3. Methyl (Z)-4-fluorooctadec-4-enoate (7c)
According to the general procedure, from allylic alcohol
4c (258 mg, 1.00 mmol) the ester 7c was formed as a white
2
28.8 (t, C-5–C-12, C-14), 73.1 (dd, JC,F = 29.2 Hz, C-1),
111.6 (dd, 2JC,F = 14.0 Hz, C-3), 155.0 (d, 1JC,F = 255.6 Hz,
C-2), 173.4 (s, C-13). 19F NMR (CDCl3): d À127.9 (dd, 3JH,F
1
waxy solid. Yield: 248 mg (81%). m.p. 32 8C. H NMR
3
= 24.8 Hz, JH,F = 36.2 Hz).
(CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 18-CH3), 1.26 (m, 22
H, 7-CH2–17-CH2), 2.15 (m, 2 H, 6-CH2), 2.68 (m, 4 H, 2-
3
4.7. General procedure for the Johnson-Claisen
rearrangement
CH2 and 3-CH2), 3.67 (s, 3 H, 19-CH3), 4.53 (dt, JH,F
=
37.7 Hz, 3JH,H = 7.4 Hz, 1 H, 5-CH). 13C NMR (CDCl3): d
14.0 (q, C-18), 22.7 (t, C-17), 23.5 (dt, 3JC,F = 5.1 Hz, C-6),
27.5 (dt, 2JC,F = 29.3 Hz, C-3), 29.1, 29.3, 29.4, 29.6, 29.6,
31.2, 31.9 (t, C-7–C-16 and C-2), 51.5 (q, C-19), 106.1 (dd,
2JC,F = 15.3 Hz, C-5), 157.6 (d, 1JC,F = 253.0 Hz, C-4), 172.7
(s, C-1). 19F NMR (CDCl3): d À112.1 (m). GC/MS (70 eV):
m/z (%) 314 (1) [M+], 294 (8) [M+ À HF], 262 (4), 220 (13),
180 (6), 145 (24) [M+ À C12H25], 132 (21) [M+ + H À
C13H27], 97 (34) [C7H13+], 85 (42) [C6H13+], 74 (100)
In a 10 mL round bottom flask a solution of the
corresponding alcohol (1 mmol), trimethyl orthoacetate
(1.47 mL) and one drop of propanoic acid was refluxed in
dry toluene (2 mL) for 5 h. After cooling to room
temperature, the mixture was poured into water (20 mL)
and the aqueous phase was extracted with diethyl ether (3 Â
10 mL). The combined ethereal extract was washed with
brine (10 mL) and dried over MgSO4. The product was
purified by column chromatography (silica gel, cyclohex-
ane/ethyl acetate, 20:1).
+
+
[C3H6O2 ], 69 (23) [C5H11+], 67 (17) [C6H9 ], 57 (27)
+
+
+
+
[C4H9 ], 55 (25) [C4H7 ], 43 (41) [C3H7 ], 41 (33) [C3H5 ].
Calcd. for C19H35FO2 (314.26): C 72.57, H 11.22. Found: C
72.50, H 11.43.
4.7.1. Methyl (Z)-4-fluoroct-4-enecarboxylate (7a)
According to the general procedure, from allylic alcohol
4a (118 mg, 1.00 mmol), the ester 7a was formed. Yield:
170 mg (96%). 1H NMR (CDCl3): d 0.89 (t, 3JH,H = 7.2 Hz, 3
H, 8-CH3), 1.35 (m, 2 H, 7-CH2), 2.03 (m, 2 H, 6-CH2), 2.48
4.7.4. Ethyl 3-(1-fluoroethenyl)-decanoate (8)
According to the general procedure, the allylic alcohol 6
(174 mg, 1.00 mmol) was refluxed with triethyl orthoacetate
(1 mL) and one drop of propanoic acid for 20 h. After work-

1604
F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
2
48.4 Hz, 1 H, 1-CH2), 4.57 (dd, JH,H = 3.1 Hz, JH,F
3
up the residue was purified by HPLC using a RP-18 column
and methanol to give the ester 8 as a colorless liquid. Yield:
94 mg (39%). 1H NMR (CDCl3): d 0.79 (t, 3JH,H = 6.7 Hz, 3
H, 12-CH3), 1.16 (t, 3JH,H = 7.2 Hz, 3 H, 14-CH3), 1.18 (m,
=
=
3
3
16.7 Hz, 1 H, 1-CH2), 5.13 (dt, JH,H = 6.9 Hz, JH,F
18.1 Hz, 1 H, 3-CH). 13C NMR (CDCl3): d À2.9 (q, C-13),
À1.4 (q, C-13), 14.1 (q, C-10), 22.6 (t, C-9), 25.0 (t, C-5),
26.9 (t, C-12), 29.1 (t, C-7), 29.1 (t, C-6), 31.1 (t, C-4), 31.8
2
3
12 H, 6-CH2–11-CH2), 2.28 (dd, JH,H = 15.5 Hz, JH,H
=
=
=
=
=
2
6.9 Hz, 1 H, 2-CH2), 2.41 (dd, JH,H = 15.5 Hz, JH,H
3
2
2
(t, C-8), 71.0 (ds, JC,F = 30.5 Hz, C-3), 92.8 (dt, JC,F =
17.8 Hz, C-1), 162.9 (d, 1JC,F = 262.0 Hz, C-2), 171.9 (s, C-
11). 19F NMR (CDCl3): d À112.1 (m). GC/MS (70 eV): m/z
(%) 288 (0.2) [M+], 273 (0.7) [M+ À CH3], 259 (4) [M+ À
C2H5], 246 (18) [M+ À C3H6], 204 (14), 156 (6) [C10H17F+
(McLafferty)], 115 (100) [C5H11OSi+], 75 (38) [C2H7OSi+],
3
7.6 Hz, 1 H, 2-CH2), 2.61 (m, 1 H, 3-CH), 4.04 (q, JH,H
2
7.2 Hz, 2 H, 13-CH2), 4.18 (dd, JH,H = 2.9 Hz, JH,F
3
2
3
50.3 Hz, 1 H, 5-CH2), 4.45 (ddd, JH,H = 2.9 Hz, JH,F
16.7 Hz, 4JH,H = 0.5 Hz, 1 H, 5-CH2). 13C NMR (CDCl3): d
14.0 (q, C-12), 14.2 (q, C-14), 22.6 (t, C-11), 26.8 (t, C-6),
29.1, 29.3 (t, C-7 and C-9), 31.5 (t, C-8), 31.8 (t, C-10), 37.4
(t, C-2), 39.2 (dd, 2JC,F = 25.4 Hz, C-3), 60.4 (t, C-13), 90.5
73 (77) [C3H9Si+], 55 (19) [C4H7 ], 43 (38) [C3H7 ].
+
+
(dt, 2JC,F = 20.4 Hz, C-5), 167.1 (d, 1JC,F = 260.7 Hz, C-4),
4.8.2. (Z)-2-Chloro-4-fluorooct-4-enoic acid (15a)
3
171.8 (s, C-1). 19F NMR (CDCl3): d À106.2 (ddd, JH,F
=
According to general procedure the ester 10a (398 mg,
2.00 mmol) was rearranged. Different from the general
procedure the combined ethereal phase was extracted with
1N NaOH (3 Â 15 mL) and the ethereal phase was trashed.
The basic solution was acidified with conc. HCl and
extracted with diethyl ether (3 Â 15 mL). The combined
ethereal layer was washed with water (15 mL) and dried
over MgSO4. After evaporation of the solvent the product
15a was isolated without further purification. Yield: 110 mg
(29%). 1H NMR (CDCl3): d 0.90 (t, 3JH,H = 7.4 Hz, 3 H, 8-
CH3), 1.38 (tq, 3JH,H = 7.4 Hz, 3JH,H = 7.2 Hz, 2 H, 7-CH2),
19.1 Hz, 3JH,F = 22.9 Hz, 3JH,F = 51.5 Hz). GC/MS (70 eV):
m/z (%) 244 (0) [M+], 224 (1) [M+ À HF], 216 (0) [M+ À
C2H4 (McLafferty)], 201 (1) [216 À CH3], 195 (2), 181 (2)
[216 À HF À CH3], 167 (5) [M+ À HF À C4H9], 156 (1)
[C10H17F+ (McLafferty)], 146 (28) [M+ À C7H14], 156 (16)
[156 À HF], 111 (19), 99 (17) [C7H15+], 95 (19), 93 (20), 81
+
+
+
(27), 73 (100) [C3H5O2 ], 57 (29) [C4H9 ], 55 (56) [C4H7 ],
+
43 (61) [C3H7 ], 41 (72) [C3H5 ].
+
4.8. General procedure for the Ireland-Claisen
rearrangement
2
3
2.07 (m, 2 H, 6-CH2), 2.71 (ddd, JH,H = 15.0 Hz, JH,H
2
=
=
3
7.8 Hz, JH,F = 22.7 Hz, 1 H, 3-CH2), 2.96 (ddd, JH,H
In a dried Schlenk vessel the respective allylic ester
(2.00 mmol) in CH2Cl2 (4 mL) was treated under argon with
triethylamine (0.60 g, 6.0 mmol) and TMSOTf (0.46 g,
2.4 mmol) and stirred at room temperature for 4 days, while
the solution turned from colorless to dark red-brown. Then
2N HCl (15 mL) was added and the mixture was stirred
vigorously for 4 h. The phases were separated and the
aqueous was extracted with diethyl ether (3 Â 15 mL).
Further work-up was different for the respective products
and will be mentioned below.
15.0 Hz, 3JH,H = 6.2 Hz, 3JH,F = 15.0 Hz, 1 H, 3-CH2), 4.49
(dd, 3JH,H = 7.8 Hz, 3JH,H = 6.4 Hz, 1 H, 2-CHCl), 4.72 (dt,
3JH,H = 7.5 Hz, 3JH,F = 37.3 Hz, 1 H, 5-CH), 10.50 (br s, 1 H,
COOH). 13C NMR (CDCl3): d 13.5 (q, C-8), 22.4 (t, C-7),
25.6 (dt, 3JC,F = 3.8 Hz, C-6), 37.9 (dt, 2JC,F = 28.0 Hz, C-3),
2
53.1 (d, C-2), 110.1 (dd, JC,F = 14.0 Hz, C-5), 153.3 (d,
1JC,F = 251.8 Hz, C-4), 174.7 (s, C-1). 19F NMR (CDCl3): d
3
3
3
À114.3 (ddd, JH,H = 17.2 Hz, JH,F = 22.9 Hz, JH,F
=
38.1 Hz). GC/MS (70 eV) (TMS-Ester): m/z (%) 267 (1) [M+
+ H], 266 (1) [M+], 253/251 (5/1) [M+ À CH3], 231 (32) [M+
À Cl], 215 (31) [M+ À HCl À CH3], 187 (6), 173 (12), 168/
166 (12/6) [C5H11O2SiCl+ (McLafferty)], 150 (15), 141 (36)
[M+ À HCl À (CH3)3SiO], 121 (9) [141 À HF], 99 (12), 93
(32), 77 (39), 73 (100) [(CH3)3Si+], 45 (12).
4.8.1. 3-(Trimethylsilylacetoxy)-2-fluorodecene (14)
According to general procedure for the Ireland-Claisen
rearrangement, the ester 9b (0.43 g, 2.0 mmol) in dry diethyl
ether (4 mL) was stirred with triethylamine (0.61 g,
6.0 mmol) and TMSOTf (0.46 g, 2.4 mmol) at room
temperature for 4 days. The brown mixture was hydrolysed
with water (20 mL) and extracted with diethyl ether (2 Â
20 mL). After washing the combined ethereal phase with
water (20 mL) and drying over MgSO4, the solvent was
evaporated and the residue was filtered through a silica gel
column (pentane/diethyl ether, 15:1) to get a colorless oil.
Yield: 0.42 g containing 28% of starting material 9b and
72% of 14. This mixture could not be separated. NMR
spectroscopic data of compound 14 were extracted from the
spectra of this mixture. 1H NMR (CDCl3): d 0.00 (s, 9 H, 13-
4.8.3. (Z)-2-Chloro-4-fluorododec-4-enoic acid (15b)
According to general procedure the ester 10b (625 mg,
2.50 mmol) was rearranged and the product 15b was isolated
1
as described for compound 15a. Yield: 340 mg (54%). H
NMR (CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 12-CH3), 1.27
(m, 10 H, 7-CH2–11-CH2), 2.07 (m, 2 H, 6-CH2), 2.71 (m, 1
H, 3-CH2), 2.97 (m, 2 H, 3-CH2), 4.49 (dd, 3JH,H = 7.6 Hz,
3JH,H = 6.7 Hz, 1 H, 2-CHCl), 4.71 (dt, 3JH,H = 7.5 Hz, 3JH,F
= 37.4 Hz, 1 H, 5-CH). 13C NMR (CDCl3): d 14.0 (q, C-12),
22.6 (t, C-11), 23.6 (dt, 3JC,F = 5.1 Hz, C-6), 29.0, 29.1, 29.5
(t, C-7–C-9), 31.8 (t, C-10), 37.9 (dt, 2JC,F = 28.0 Hz, C-3),
CH3), 0.75 (t, 3JH,H = 6.7 Hz, 3 H, 10-CH3), 1.14 (m, 10 H,
53.0 (d, C-2), 110.5 (dd, JC,F = 15.3 Hz, C-5), 153.1 (d,
1JC,F = 251.8 Hz, C-4), 174.4 (s, C-1). 19F NMR (CDCl3): d
2
2
5-CH2–9-CH2), 1.59 (m, 2 H, 4-CH2), 1.80 (d, JH,H
=
=
2
1.9 Hz, 2 H, 12-CH2), 4.42 (dd, JH,H = 3.1 Hz, JH,F
3
3
3
3
À114.5 (ddd, JH,F = 15.3 Hz, JH,F = 22.9 Hz, JH,F
=

F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
1605
3
3
38.2 Hz). GC/MS (70 eV) (TMS-Ester): m/z (%) 322 (1)
[M+], 307 (4) [M+ À CH3], 287 (42) [M+ À Cl], 271 (17) [M+
À HCl À CH3], 250 (1) [M+ + H À TMS], 227 (1), 197 (11),
(CDCl3): d À114.4 (ddd, JH,F = 17.2 Hz, JH,F = 22.9 Hz,
3JH,F = 38.2 Hz). GC/MS (70 eV) (TMS-Ester): m/z (%) 406
(1) [M+], 391 (3) [M+ À CH3], 371 (34) [M+ + H À Cl], 370 (6)
[M+ À Cl], 355 (22) [370 À CH3], 311 (1), 281 (6), 252 (2),
233 (2), 173 (8), 166 (43) [C5H11O2Si+], 150 (28), 117 (14)
166 (33), 150 (23), 73 (100) [(CH3)3Si+], 42 (26) [C3H7 ].
+
+
+
+
4.8.3.1. Methyl (Z)-2-chloro-4-fluorododec-4-enoate. (Z)-
2-Chloro-4-fluorododec-4-enoic acid (15b) (250 mg,
1.00 mmol) and methanol (35.2 mg, 1.10 mmol) were
dissolved in pentane (50 mL). DCC (228 mg, 1.1 mmol)
and a catalytic amount of DMAP were added and the
mixture was stirred at room temperature overnight. The
resulting suspension was filtered and the colorless solution
was washed with water (3 Â 20 mL), 5% aqueous acetic acid
(3 Â 20 mL) and again with water (20 mL). The solution
was dried over MgSO4, the solvent was removed and the
residue was purified by column chromatography (silica gel,
cyclohexane/ethyl acetate, 20:1) and the ester was isolated
as a colorless liquid. Yield: 228 mg (86%). 1H NMR
(CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 12-CH3), 1.27 (m, 10
[COOSiCH3 ], 73 (100) [SiCH3 ], 57 (22) [C4H9 ], 55 (26)
+
[C4H7 ], 43 (32) [C3H7 ], 41 (23) [C3H5 ].
+
+
4.8.5. 2-Chloro-4-fluoropent-4-enoic acid (15d)
According to general procedure the ester 10d (152 mg,
1.00 mmol) was rearranged and the product 15d was isolated
without further purification. Yield: 130 mg (86%). 1H NMR
(CDCl3): d 2.79 (ddd, 2JH,H = 15.3 Hz, 3JH,H = 8.1 Hz, 3JH,F
= 23.1 Hz, 1 H, 3-CH2), 3.01 (ddd, 2JH,H = 14.6 Hz, 3JH,H
=
6.0 Hz, 3JH,F = 14.6 Hz, 1 H, 3-CH2), 4.36–4.59 (m, 2 H, 2-
CHCl and 5-CH2), 4.75 (dd, 2JH,H = 3.1 Hz, 3JH,F = 16.7 Hz,
1 H, 5-CH2), 7.61 (br s, 1 H, COOH). 13C NMR (CDCl3): d
37.6 (dt, 2JC,F = 29.2 Hz, C-3), 52.6 (d, C-2), 94.1 (dt, 2JC,F
=
19.1 Hz, C-5), 160.4 (d, 1JC,F = 256.9 Hz, C-4), 173.4 (s, C-
1). 19F NMR (CDCl3): d À99.2 (m). GC/MS (70 eV) (TMS-
Ester): m/z (%) 226/224 (0.5/1) [M+], 211/209 (3/7) [M+ À
CH3], 189 (15) [M+ À Cl], 173 (4) [M+ À HCl À CH3], 167
(1), 137 (2), 117 (5) [C4H9O2Si+], 99 (7) [M+ À HCl À
(CH3)3SiO], 93 (39), 73 (100) [(CH3)3Si+], 53 (23).
H, 7-CH2–11-CH2), 2.05 (m, 2 H, 6-CH2), 2.70 (ddd, 2JH,H
=
15.3 Hz, 3JH,H = 8.1 Hz, 3JH,F = 22.7 Hz, 1 H, 3-CH2), 2.92
(ddd, 2JH,H = 15.3 Hz, 3JH,H = 6.7 Hz, 3JH,F = 15.3 Hz, 1 H,
3
3-CH2), 3.79 (s, 3 H, 13-CH3), 4.44 (dd, JH,H = 6.7 Hz,
3JH,H = 7.9 Hz, 1 H, 2-CH), 4.68 (dt, 3JH,H = 7.6 Hz, 3JH,F
=
37.4 Hz, 1 H, 5-CH). 13C NMR (CDCl3): d 14.0 (q, C-12),
22.6 (t, C-11), 23.6 (dt, 3JC,F = 3.1 Hz, C-6), 29.0, 29.0, 29.2
(t, C-7–C-9), 31,8 (t, C-10), 51.6 (d, C-2), 53.1 (q, C-13),
110.1 (dd, 2JC,F = 14.0 Hz, C-5), 153.5 (d, 1JC,F = 251.8 Hz,
C-4), 176.0 (s, C-1). 19F NMR (CDCl3): d À114.2 (ddd, 3JH,F
4.8.6. 2-Chloro-3-(1-fluoroethenyl)-decanoic acid (17)
According to the general procedure the ester 12 (250 mg,
1.00 mmol) was rearranged. After chromatography (silica
gel, cyclohexane/ethyl acetate/acetic acid) the 1:1 mixture
of 17 was isolated as a colorless liquid. Yield: 150 mg
(60%). 1H NMR (CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 12-
CH3), 1.28 (m, 10 H, 7-CH2–11-CH2), 1.35–1.51 and 1.51–
1.68 (m, 2 H, 6-CH2), 2.82 (m, 1 H, 3-CH), 4.31 and 4.38 (d,
3JH,H = 8.6 Hz and 3JH,H = 8.1 Hz, 1 H, 2-CH), 4.43 and 4.45
(dd, 2JH,H = 3.1 Hz, 3JH,F = 49.8 Hz and 2JH,H = 3.1 Hz, 3JH,F
= 49.8 Hz, 1 H, 5-CH2), 4.75 and 4.78 (dd, 2JH,H = 3.1 Hz,
3
3
= 15.3 Hz, JH,F = 21.0 Hz, JH,F = 38.2 Hz). GC/MS
(70 eV): m/z (%) 266/264 (1/2) [M+], 229 (93) [M+ À Cl],
228 (23) [M+ À HCl], 209 (4) [M+ À HF À Cl], 208 (4) [M+
À HF À HCl], 177 (5), 157 (8) [C10H18F+], 131 (40), 110/
108 (28/100) [C3H5O2Cl+ (McLafferty)], 81 (26), 59 (29)
+
+
+
[C2H3O2 ], 55 (34) [C4H7 ], 43 (56) [C3H7 ], 41 (32)
+
[C3H5 ].
3JH,F = 17.4 Hz and ddd, JH,H = 3.1 Hz, JH,F = 17.6 Hz,
4JH,H = 0.5 Hz, 1 H, 5-CH2), 9.81 (br s, 1 H, COOH). 13C
NMR (CDCl3): d 14.0 (q, C-12), 22.6, 26.6, 27.0, 27.6, 28.5,
2
3
4.8.4. (Z)-2-Chloro-4-fluorooctadec-4-enoic acid (15c)
According to general procedure the ester 10c (541 mg,
1.61 mmol) was rearranged. The combined ethereal extract
was washed with brine (2 Â 15 mL), dried over MgSO4, and
the solvent was removed. The crude product was purified by
HPLC using an RP-18 column and methanol as the solvent.
The carboxylic acid 15c was isolated as a white solid. Yield:
353 mg (66%). m.p. 48 8C. 1H NMR (CDCl3): d 0.88 (t, 3JH,H
= 6.6 Hz, 3 H, 18-CH3), 1.26 (m, 22 H, 7-CH2–17-CH2), 2.08
(dt, 3JH,H = 6.7 Hz, 3JH,H = 6.9 Hz, 2 H, 6-CH2), 2.72 (ddd,
2JH,H = 15.0 Hz, 3JH,H = 7.9 Hz, 3JH,F = 21.9 Hz, 1 H, 3-CH2),
2.96 (ddd, 2JH,H = 15.0 Hz, 3JH,H = 6.2 Hz, 3JH,F = 21.2 Hz, 1
H, 3-CH2), 4.47 (dd, 3JH,H = 6.2 Hz, 3JH,H = 7.9 Hz, 1 H, 2-
29.0, 29.1, 29.2, 31.7, 31.7 (t, C-6–C-11), 46.8 (dd, 2JC,F
=
25.4 Hz, C-3), 47.1 (dd, 2JC,F = 25.4 Hz, C-3), 56.9 (d, C-1),
58.5 (d, C-2), 94.2 (dt, 2JC,F = 19.1 Hz, C-5), 95.7 (dt, 2JC,F
=
1
19.1 Hz, C-5), 162.2 (d, JC,F = 260.5 Hz, C-4), 162.9 (d,
1JC,F = 260.7 Hz, C-4), 174.1 (s, C-1), 174.3 (s, C-1). 19F
3
3
NMR (CDCl3): d À107.8 (ddd, JH,F = 19.1 Hz, JH,F
=
=
3
3
24.8 Hz, JH,F = 51.5 Hz, 0.5 F), À105.2 (ddd, JH,F
3
3
17.2 Hz, JH,F = 22.9 Hz, JH,F = 49.6 Hz, 0.5 H). GC/MS
(70 eV) (TMS-Ester): m/z (%) 325/323 (0/1) [M+ + H], 324/
322 (0/1) [M+], 287 (10) [M+ À Cl], 265 (3) [M+ À H À HCl
À HF], 252 (2), 223 (13) [M+ À C7H15], 189 (6), 173 (3), 166
(2) [C5H11O2SiCl+ (McLafferty)], 150 (6), 131 (9) [166 À
3
3
CH), 4.71 (dt, JH,H =7.6 Hz, JH,F = 37.2 Hz, 1 H, 5-CH),
9.45 (br s, 1 H, COOH). 13C NMR (CDCl3): d 14.1 (q, C-18),
22.7 (t, C-17), 23.6 (dt, 3JC,F = 3.8 Hz, C-6), 29.1, 29.1, 29.4,
Cl], 73 (100) [(CH3)3Si+], 55 (18) [C4H7 ], 41 (17) [C3H5 ].
+
+
29.6, 29.6, 29.7 (t, C-7–C-15), 31.9 (t, C-16), 38.0 (dt, 2JC,F
=
4.8.7. (Z)-4-Fluoro-2-methyloct-4-enoic acid (16a)
According to general procedure the ester 11a (348 mg,
2.00 mmol) was rearranged. After work-up as described for
29.2 Hz, C-3), 53.1 (d, C-2), 110.4 (dd, 2JC,F = 14.0 Hz, C-5),
1
153.2 (d, JC,F = 251.8 Hz, C-4), 174.3 (s, C-1). 19F NMR

1606
F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
compound 15a the product 16a was isolated without further
purification. Yield: 110 mg (32%). 1H NMR (CDCl3): d 0.89
(t, 3JH,H = 7.2 Hz, 3 H, 8-CH3), 1.22 (d, 3JH,H = 6.9 Hz, 3 H,
was isolated as a colorless liquid. Yield: 163 mg (67%). 1H
NMR (CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 12-CH3), 1.18
(d, 3JH,H = 6.9 Hz, 3 H, 13-CH3), 1.27 (m, 10 H, 7-CH2–11-
2
9-CH3), 1.30–1.44 (m, 2 H, 7-CH2), 2.03 (m, 2 H, 6-CH2),
3
CH2), 2.05 (m, 2 H, 6-CH2), 2.21 (ddd, JH,H = 14.6 Hz,
3
2.15–2.79 (br m, 3 H, 2-CH and 3-CH2), 4.57 (dt, JH,H
=
3JH,H = 7.6 Hz, JH,F = 21.7 Hz, 1 H, 3-CH2), 2.54 (ddd,
7.5 Hz, 3JH,F = 37.5 Hz, 1 H, 5-CH), 9.75 (br s, 1 H, COOH).
13C NMR (CDCl3): d 13.5 (q, C-8), 16.2 (q, C-9), 22.5 (t, C-
7), 25.5 (dt, 3JC,F = 4.0 Hz, C-6), 35.8 (dt, 2JC,F = 28.0 Hz, C-
3), 36.9 (d, C-2), 107.6 (dd, 2JC,F = 15.3 Hz, C-5), 156.6 (d,
1JC,F = 251.8 Hz, C-4), 182.0 (s, C-1). 19F NMR (CDCl3): d
2JH,H = 14.6 Hz, JH,H = 6.7 Hz, JH,F = 17.2 Hz, 1 H, 3-
CH2), 2.71 (m, 1 H, 2-CH), 3.67 (s, 3 H, 14-CH3), 4.53 (dt,
3JH,H = 7.4 Hz, 3JH,F = 37.7 Hz, 5-CH). 13C NMR (CDCl3): d
3
3
14.0 (q, C-12), 16.4 (q, C-13), 22.6 (t, C-11), 23.5 (dt, 3JC,F
=
5.1 Hz, C-6), 29.0, 29.0, 29.4 (t, C-7–C-9), 31.8 (t, C-10),
36.2 (dt, 2JC,F = 29.2 Hz, C-3), 36.9 (d, C-2), 51.6 (q, C-14),
107.5 (dd, 2JC,F = 15.3 Hz, C-4), 156.7 (d, 1JC,F = 251.8 Hz,
C-5), 176.0 (s, C-1). 19F NMR (CDCl3): d À111.8 (ddd, 3JH,F
3
3
3
À111.8 (ddd, JH,F = 17.2 Hz, JH,F = 21.0 Hz, JH,F
=
38.1 Hz). GC/MS (70 eV) (TMS-Ester): m/z (%) 246 (3)
[M+], 231 (6) [M+ À CH3], 211 (7) [M+ À HF À CH3], 203
(1) [M+ À C3H7], 175 (8), 146 (60) [C6H14O2Si+], 130 (34)
[M+ + H À COOTMS], 109 (10) [M+ À HF À COOTMS], 99
3
3
= 17.2 Hz, JH,F = 21.0 Hz, JH,F = 38.2 Hz). GC/MS
(70 eV): m/z (%) 244 (12) [M+], 224 (2) [M+ À HF], 213 (1)
[M+ À CH3O], 209 (4) [224 À CH3], 175 (2), 159 (9) [M+ À
C6H13], 157 (13) [C10H18F+], 137 (21) [157 À HF], 111 (29),
+
(22), 73 (100) [(CH3)3Si+], 56 (24), 41 (13) [C3H5 ].
+
4.8.8. (Z)-4-Fluoro-2-methyldodec-4-enoic acid (16b)
According to general procedure the ester 11b (920 mg,
4.00 mmol) was rearranged. The ethereal solution was
extracted with 1N NaOH (3 Â 30 mL) and the organic layer
was discarded. The basic solution was acidified with conc.
HCl and extracted with diethyl ether (3 Â 30 mL). The
combined ethereal phase was dried and the solvent was
evaporated. The product 16b was isolated without further
purification. Yield: 640 mg (70%). 1H NMR (CDCl3): d 0.88
88 (100) [C4H8O2 (McLafferty)], 81 (39), 59 (18)
+
[C2H3O2 ], 57 (15) [C4H9 ], 55 (30) [C4H7 ], 43 (27)
+
+
+
+
[C3H7 ], 41 (28) [C3H5 ]. Calcd. for C12H25O2F (244.18): C
68.85, H 10.25. Found: C 68.88, H 10.34.
4.8.9. 2-Methyl-4-oxododecanoic acid (27)
According to the above-mentioned procedure the ester
11b (829 mg, 3.60 mmol) was rearranged and the crude
product 16b was subjected to column chromatography under
acidic conditions (silica gel, cyclohexane/ethyl acetate/
acetic acid, 10:1:1) to get 27 as a colorless oil. Yield: 370 mg
(45%). 1H NMR (CDCl3): d 0.88 (t, 3JH,H = 6.6 Hz, 3 H, 12-
CH3), 1.21 (d, 3JH,H = 7.2 Hz, 3 H, 13-CH3), 1.27 (m, 12 H,
6-CH2–11-CH2), 1.57 (m, 2 H, 5-CH2), 2.43 (m, 2 H, 3-
CH2), 2.95 (m, 1 H, 2-CH). 13C NMR (CDCl3): d 14.0 (q, C-
12), 16.8 (q, C-13), 22.6 (t, C-11), 23.7 (t, C-6), 29.0, 29.1,
29.3 (t, C-7–C-9), 33.5 (d, C-2), 34.5 (t, C-10), 42.9 (t, C-5),
45.4 (t, C-3), 181.5 (s, C-1), 208.9 (s, C-4). GC/MS (70 eV)
(TMS ester): m/z (%) 300 (1) [M+], 285 (27) [M+-CH3], 257
(7), 202 (37), 187 (46) [M+-C8H17], 112 (100) [C8H16+], 75
(t, 3JH,H = 6.9 Hz, 3 H, 12-CH3), 1.21 (d, 3JH,H = 6.9 Hz, 3 H,
3
13-CH3), 1.27 (m, 10 H, 7-CH2–11-CH2), 2.05 (dt, JH,H
=
6.9 Hz, 3JH,H = 6.7 Hz, 6-CH2), 2.23 (ddd, 2JH,H = 14.5 Hz,
3JH,H = 7.6 Hz, 3JH,F = 22.2 Hz, 1 H, 3-CH2), 2.65 (m, 2 H, 2-
CH and 3-CH2), 4.57 (dt, 3JH,H = 7.4 Hz, 3JH,F = 37.7 Hz, 1
H, 5-CH), 11.51 (br s, 1 H, COOH). 13C NMR (CDCl3): d
14.0 (q, C-12), 16.1 (q, C-13), 22.6 (t, C-11), 23.5 (dt, 3JC,F
5.1 Hz, C-6), 29.1, 29.4 (t, C-7–C-9), 31.8 (t, C-10), 35.8 (dt,
=
2
2JC,F = 28.0 Hz, C-3), 36.9 (d, C-2), 107.9 (dd, JC,F
=
15.3 Hz, C-5), 156.4 (d, 1JC,F = 251.8 Hz, C-4), 182.3 (s, C-
1). 19F NMR (CDCl3): d À112.2 (ddd, 3JH,F = 15.3 Hz, 3JH,F
3
= 21.0 Hz, JH,F = 38.1 Hz). GC/MS (70 eV): m/z (%) 230
+
(47) [C2H7OSi+], 73 (100) [C3H9Si+], 57 (31) [C4H9 ], 55
(12) [M+], 210 (5) [M+ À HF], 157 [C10H18F+], 137 (38)
(14) [C4H7 ], 43 (26) [C3H7 ], 41 (21) [C3H5 ].
+
+
+
[157 À HF], 125 (24) [C9H17+], 97 (10) [C7H13+], 95 (41), 81
+
+
(49), 74 (62) [C3H6O+], 55 (100) [C4H7 ], 43 (53) [C3H7 ],
4.8.10. (Z)-4-Fluoro-2-methyloctadec-4-enoic acid (16c)
According to general procedure the ester 11c (314 mg,
1.00 mmol) was rearranged. The combined ethereal extract
was washed with brine (2 Â 15 mL), dried over MgSO4, and
the solvent was removed. The crude product was purified by
HPLC using an RP-18 column and methanol as the solvent.
The carboxylic acid 16c was isolated as a white solid. Yield:
+
41 (51) [C3H5 ]. Calcd. for C13H23FO2 (230.17): C 67.79, H
10.07; Found: C 67.63, H 10.41.
4.8.8.1. Methyl (Z)-4-fluoro-2-methyldodec-4-enoate. (Z)-
4-Fluoro-2-methyldodec-4-enoic acid (16b) (230 mg,
1.00 mmol) and methanol (35 mg, 1.10 mmol) were
dissolved in pentane (50 mL). DCC (228 mg, 1.1 mmol)
and a catalytic amount of DMAP were added and the
mixture was stirred at room temperature overnight. The
resulting suspension was filtered and the colorless solution
was washed with water (3 Â 20 mL), 5% aqueous acetic
acid (3 Â 20 mL) and again with water (20 mL). The
solution was dried over MgSO4, the solvent was removed
and the residue was purified by column chromatography
(silica gel, cyclohexane/ethyl acetate, 20:1) and the ester
1
225 mg (72%). m.p. 33 8C. H NMR (CDCl3): d 0.88 (t,
3JH,H = 6.7 Hz, 3 H, 18-CH3), 1.22 (d, 3JH,H = 6.9 Hz, 3 H,
19-CH3), 1.26 (m, 22 H, 7-CH2–17-CH2), 2.04 (m, 2 H,
3
2
3-CH), 2.22 (ddd, JH,H = 7.6 Hz, JH,H = 14.6 Hz, JH,F
3
=
21.9 Hz, 1 H, 3-CH2), 2.53–2.80 (m, 2 H, 3-CH2 and 2-CH),
4.55 (dt, JH,H = 7.4 Hz, JH,F = 37.4 Hz, 1 H, 5-CH). 13C
NMR (CDCl3): d 14.1 (q, C-18), 16.2 (q, C-19), 22.7 (t, C-
3
3
3
17), 23.5 (dt, JC,F = 3.8 Hz, C-6), 29.1, 29.1, 29.3, 29.4,
29.4, 29.6, 29.7 (t, C-7–C-15), 31.9 (t, C-16), 35.8 (dt, 2JC,F

F. Tranel, G. Haufe / Journal of Fluorine Chemistry 125 (2004) 1593–1608
1607
= 28.0 Hz, C-3), 36.8 (d, C-2), 107.9 (dd, 2JC,F = 15.3 Hz, C-
5), 156.4 (d, 1JC,F = 251.8 Hz, C-4), 181.7 (c, C-1). 19F NMR
References
3
3
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(5) [M+], 371 (3) [M+ À CH3], 366 (2) [M+ À HF], 351 (18)
[366 À CH3], 315 [M+ À C4H10Si], 287 (1), 217(3), 183 (4)
[C13H27+], 169 (5) [C12H25+], 146 (100) [C6H14O2Si+], 131
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4.8.11. 4-Fluoro-2-methylpent-4-enoic acid (16d)
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(5%). H NMR (CDCl3): d 1.18 (d, 3JH,H = 6.9 Hz, 3 H, 6-
2
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3
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3
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4.8.12. 3-(1-Fluoroethenyl)-2-methyldecanoic acid (18)
According to the general procedure the ester 13 (216 mg,
0.94 mmol) was rearranged. The acid 18 was isolated as a
colorless liquid by column chromatography (silica gel,
cyclohexane/ethyl acetate/acetic acid, 10:1:2) as a 81:19
mixture of diastereomers. The isomers could not be
separated by HPLC. Yield: 120 mg (56%); 62% de. 1H
NMR (CDCl3): d 0.88 (t, 3JH,H = 6.9 Hz, 3 H, 12-CH3), 1.19
(d, 3JH,H = 7.2 Hz, 3 H, 13-CH3), 1.27 (m, 10 H, 7-CH2–11-
CH2), 1.45 (m, 2 H, 6-CH2), 2.53 (m, 1 H, 3-CH), 2.70 (m, 1
H, 2-CH), 4.30 (dd, 2JH,H = 2.9 Hz, 3JH,F = 50.3 Hz, 1 H, 5-
CH2), 4.62 (dd, 2JH,H = 2.6 Hz, 3JH,F = 17.9 Hz, 1 H, 5-CH2),
10.31 (br s, 1 H, COOH). 13C NMR (CDCl3): d 13.4 (q, C-
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C-11), 41.8 (d, C-2), 45.0 (dd, 2JC,F = 24.2 Hz, C-3), 91.8 (dt,
2JC,F = 20.3 Hz, C-5), 166.3 (d, 1JC,F = 260.7 Hz, C-4), 181.4
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Acknowledgements
This research project was supported by the Deutsche
Forschungsgemeinschaft (Graduiertenkolleg ‘‘Hochreaktive
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