Synthesis of geminal-bis(trifluoromethyl)-substituted dienes, heterodienes, 7,7,7,8,8,8-hexafluoro-β-cyclocitral and -safranal

Article abstract of DOI:10.1016/S0022-1139(99)00038-X

Reaction of 5,5,5-trifluoro-4-(trifluoromethyl)penta-3-en-2-one (1) with p-toluene-sulfonylhydrazines under basic conditions provided anti-Michael addition products. Acid-catalyzed reactions yielded the expected hydrazones. In the absence of solvent the r

Full text of DOI:10.1016/S0022-1139(99)00038-X

Journal of Fluorine Chemistry 97 (1999) 115±125
Synthesis of geminal-bis(tri¯uoromethyl)-substituted dienes,
heterodienes, 7,7,7,8,8,8-hexa¯uoro-b-cyclocitral
and -safranal
K. Brandta, A. Haasb,*, T. Hardtb, H. Mayer-Figgea,
K. Merzc, T. Wallmichrathb
È È
Lehrstuhl fur Analytische Chemie, Ruhr-Universitat Bochum, Bochum, Germany
a
b
È È È
Ruhr-Universitat Bochum, Fakultat fur Chemie, FNO 034/036, D-44780, Bochum, Germany
c
È È
Lehrstuhl fur Anorganische Chemie I, Ruhr-Universitat Bochum, Bochum, Germany
Received 24 October 1998; received in revised form 14 December 1998; accepted 15 December 1998
Dedicated to Prof. Yoshiro Kobayashi on the occasion of his 75th birthday
Abstract
Reaction of 5,5,5-tri¯uoro-4-(tri¯uoromethyl)penta-3-en-2-one (1) with p-toluene-sulfonylhydrazines under basic conditions provided
anti-Michael addition products. Acid-catalyzed reactions yielded the expected hydrazones. In the absence of solvent the reaction of
(CH3)3SiCl with 1 gave the corresponding silylenolether (3), which did not yield cross condensation products with ketones. In the presence
of TiCl4 silylenolether (3) reacted at 788C to give the corresponding nonadienone (11). Analogously at 208C condensation with water
elimination gave the pyran system (12). The yields of 11 and 12 were increased by adding ZnCl2. It is interesting to note that
trimethylsiloxycyclohexene reacted with 1 in a Mukaiyama-aldol-condensation to the corresponding cross condensation product 13.
Starting from (CF3)2C=C(CN)2 and a mixture of (E/Z)-1,3-pentadiene the expected cyclohexene was formed. One of the two CN-groups
was removed with NaOH in C2H5OH/H2O. A second double bond was introduced in an allylic position of the hexene ring by bromination
and elimination with (C2H5)3N to yield the diene. Reduction with DIBAlH provided the aldehyde 7,7,7,8,8,8-hexa¯uorosafranal.
Hydrogenation of the C3±C4 double bond in the presence of palladium on a charcoal catalyst led to 7,7,7,8,8,8-hexa¯uoro-b-cyclocitral. X-
ray structures of selected compounds are provided. # 1999 Elsevier Science S.A. All rights reserved.
Keywords: Anti-Michael addition; Bis(tri¯uoromethyl)dienes; Condensation; Hydrazines; Disilylenolethers; Nonadienone; Substituted pyran; Cycloaddi-
tions; Bis(tri¯uoromethyl)-ethylene-1,1-carbodinitrile; Hexa¯uorosafranal; Selective hydrogenation; Hexa¯uoro-b-cyclocitral; X-ray structures
1. Introduction
syn- and anti-isomers and contrary to alkylamines the
expected anti-Michael products are obtained quantitatively
[1] as shown below.
Based on recent studies [1,2] and new reactions it could be
shown that 5,5,5-tri¯uoro-4-tri¯uoromethylpent-3-en-2-one
(1) is a versatile and highly reactive educt which provides
new substances with interesting properties. Chemical reac-
tivity differs substantially from the corresponding non¯uori-
nated pentaenone. It can be prepared almost quantitatively
from (CF3)2CO and (C5H5)3P=CHC(O)CH3 in the presence
of hydroquinone without solvent [3]. Among the reactions
studied it is interesting to note that 1 yields with ring-
substituted aniline derivates, the corresponding stable bis-
tri¯uoromethylated a,b-unsaturated imines as a mixture of
With elemental bromine in CCl4 1 formed two brominated
compounds (CF3)2C=CH±C(O)CH3 nBrn (nˆ1,2) [2].
The aim of this paper is the investigation of the chemistry
of 1 and the preparation of new precursors for the synthesis
of 16,16,16,17,17,17-hexa¯uororetinals.
*Corresponding author. Tel.: +49-234-700-3003; fax: +49-234-7094-
541; e-mail: alois.haas@ruhr-uni-bochum.de
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 3 8 - X

116
K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
Scheme 1.
2. Results and discussion
drazines depends on the pH-value of the medium. Under
basic conditions 4-CH3±C6H5SO2NHNH2 is added as a
nucleophile to the C=C bond providing the anti-
Michael addition product 1,1,1-tri¯uoro-2-(tri¯uoro-
methyl)-3-(p-toluene-sulfonylhydrazine)-pent-4-one (5).
This type of addition was observed before with alkylamines
[1].
The conversion of 1 with phosphoryl chloride and triethy-
lamine without solvent leads to the diene 1,1,1-tri¯uoro-2-
(tri¯uoromethyl)-penta-2,4-dienyl-(dichlorophosphoroaci-
dester) (2), which was isolated and characterized.
Similarly the silylenolethers 1,1,1-tri¯uoro-2-(tri¯uoro-
methyl)-4-(trimethylsiloxy)-penta-2,4-diene
(3)
and
The obtained X-ray structure of 5 (Fig. 1) shows an
interesting detail. The two nitrogen atoms do not have
the expected pyramidal structure as bond angles are moving
toward planarity. This conclusion is con®rmed by the
nitrogen±nitrogen bond distance placed just between
d(N±N) of a plane±plane and a plane±pyramidal structure
as proved by the following ®gures.
dimethyl-bis-(1,1,1-tri¯uoro-2-tri¯uoromethylpenta-2,4-
dienyl-4-oxy)silane (4) are made by treating 1 with
(CH3)3SiCl or (CH3)2SiCl2, respectively, in the precence
of (C2H5)3N (see Scheme 1). Especially compounds 2
and 3 are reactive educts and are used for further investiga-
tions. The reactivity of 1 toward substituted arylsulfonylhy-

K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
117
Fig. 1. X-ray structure of 5.
Fig. 3. X-ray structure of 6b.
Selected bond angles of 5:
N(2)±N(1)±S(1)
N(2)±N(1)±H(1)
S(1)±N(1)±H(1)
N(1)±N(2)±C(4)
N(1)±N(2)±H(2)
C(4)±N(2)±N(1)
111.68
103.78
1238
112.28
1078
are not in the same plane. The torsional angles for 6a and b
are 70.18 and 41.28, respectively. These ꢀ angles show that
both are not conjugated but 6a less than 6b. This conclusion
is con®rmed by considering bond lengths. The distances
d(C1±C2) placed between d(N=C) and d(C2=C3) are more
in the range of a nonconjugated system than those of a
conjugated system as demonstrated by the following data.
Therefore, it is concluded that the double bonds in both
compounds are separated from each other.
1158
Comparison of N±N bond distance in 5 with literature data:
Ê
Ê
Ê
N(1)±N(2) found
Npyramidal±Npyramidal
Npyramidal±Nplane
Nplane±Nplane
1.415 A
1.425 A [4]
1.420 A [4]
Ê
1.401 A [4]
Comparison of bond length:
Ê
C±C (A)
Ê
C=C (A)
By changing the reaction conditions from basic to acid
catalysis, the addition of a nucleophile could be prevented. 1
reacts with p-toluene-sulfonylhydrazine and 2,4,6-triisopro-
pylbenzenesulfonylhydazine under acidic conditions to give
the corresponding 1,1,1-tri¯uoro-2-(tri¯uoromethyl)-4-(p-
toluene-sulfonylhydrazone)pent-2-ene (6a) and 1,1,1-tri-
¯uoro-2-(tri¯uoromethyl)-4-(20,40,60-triisopropylbenzene-
sulfonylhydrazone)pent-2-ene (6b) in almost quantitative
yields.
6a
6b
1.475
1.470
1.315
1.327
Conjugated system
Nonconjugated system
1.455 [5] 1.330±1.345 [7,8]
1.478 [6] 1.312±1.317 [9,10]
Both hydrazones 6a and b react with triethylamine and
iodine to give 1,1,1-tri¯uoro-2-(tri¯uoromethyl)-4-iodo-
penta-2,4-diene (7).The main product in this reaction, how-
ever, is 5-methyl-3,3-bis-(tri¯uoromethyl)-3H-pyrazole (8).
Better access to 8 is accomplished by treatment of 6a with
sodium hydroxide in a two phase system. The reaction
between 6a and nitrogen dioxide took an unexpected course.
Surprisingly oxygen is not inserted but N2-elimination is
observed providing 5,5,5-tri¯uoro-2-nitro-4-tri¯uoro-
methyl-2-(4-toluenesulfonyl)-pent-3-ene (9) which could
be recrystallized. An X-ray determination carried out on
a single crystal (Fig. 4) proved the proposed structure.
The expected F/Cl-metathesis between diethylamino sul-
furtri¯uoride (DAST) and 2 unexpectedly did not give a
¯uorinated compound but 1,1,1-tri¯uoro-2-(tri¯uoro-
methyl)-5-chloro-pent-2-en-4-one (10). Such a result for
a ¯uorination reaction was to our knowledge not observed
before.
Surprisingly the elucidated X-ray structures of 6a and b
(Figs. 2 and 3) prove that the C2=C3 and N=C double bonds
In Mukaiyama-aldol condensations, silylenolethers react
smoothly with carbonyl compounds to give the correspond-
Fig. 2. X-ray structure of 6a.

118
K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
reaction is the anti-Michael addition of the nucleophile
(a-metallated esther) in the 3-position of 1 followed by
¯uoride abstraction as shown for 16. In the next step
metallation in g-position yields the enolate which attacks
nucleophilically the ole®nic CF2-carbon forming 4-acetyl-
2-¯uoro-6-methyl-5-methoxycarbonyl-3-tri¯uoromethyl-
pyran (17) by ¯uoride abstraction.
Besides 1, 2,2-bis(tri¯uoromethyl)-ethylene-1,1-dicarbo-
nitrile (18) is an active and versatile synthon [15]. It reacts
with normal dienes as dienophile in Diels±Alder reactions
providing corresponding cyclohexenes and in some cases
the reaction rate is higher than the one of tetracyanoethy-
lene, an extremely strong dienophile. With (E)-1,3-penta-
diene 18 forms 90% 1,1-bis(tri¯uoromethyl)-5-methyl-6,6-
dicyano-cyclohex-3-ene (19) [16]. The yield can be
increased to 97% by using a slight excess of (E/Z)-mixture
and extending the reaction time from 10 to 15 min at 08C. In
order to use 19 as a precursor for the synthesis of
16,16,16,17,17,17-hexa¯uoro-retinal, the double bond has
to be shifted from position 3 to 5 and one nitrile group has to
be eliminated. The latter is accomplished by stirring 19 at
228C (5 days) with a solution of NaOH ethanol/water (2:1)
Fig. 4. X-ray structure of 9.
ing cross-condensation products [11]. However, 3 does not
perform with ketones the expected procedure. Under cata-
lytic conditions self-condensation is substantially faster
than reaction with the ketone. At 788C the corresponding
1,1,1,9,9,9-hexa¯uoro-6-hydroxy-6-methyl-2,8-bis(tri¯uor-
omethyl)-nona-2,7-dien-4-one (11) is yielded and at room
temperature under analogous catalytic conditions, water is
eliminated and 4-methyl-2,2-bis-(tri¯uoromethyl)-6-(3,3,3-
tri¯uoro-2-tri¯uoromethylpropenyl)-2H-pyran (12) is
formed. The yield is increased by adding zinc chloride to
the reaction mixture. In this context it is interesting to note
that 1 reacts with 1-trimethylsilyloxycyclohexene in a
Mukaiyama-aldol condensation to give the corresponding
cross-condensation product 2-(4,4,4-tri¯uoro-1-hydroxy-1-
methyl-3-tri¯uoromethylbut-2-enyl)cyclohexanone (13).
Also in this case the yield could be increased by adding
zinc chloride.
Conversion of 1 to a higher ¯uorinated alkene is accom-
plished by ¯uorination with sulfur tetra¯uoride. In the
presence of anhydrous HF as a catalyst and solvent
1,1,1,4,4-penta¯uoro-2-tri¯uoromethylpent-2-ene (14) is
provided.
Nucleophilic reagents such as NH3 add on the C=C
double bond of 14 according to anti-Michael addition as
was shown before for 1 [1]. The preparation of 1,1,1,4,4-
penta¯uoro-2-tri¯uoromethyl-3-aminopentane (15) is
accomplished by treating 14 with NaNH2 in the presence
of H2O.
providing
(5-R,6-S/5-S,6-R)-1,1-bis(tri¯uoro-methyl)-5-
methyl-6-cyanocyclohex-3-ene (20) in 97% yield. The shift
of the double bond is possible by bromination with N-
bromosuccinimide substituting an allylic position and after-
wards eliminating HBr with (C2H5)3N yielding 1,1-bis(tri-
¯uoromethyl)-5-methyl-6-cyanocyclohexa-3,5-diene (21).
Starting from 21 new hexa¯uorinated natural products
can be obtained, e.g. by reduction with diisobutylalumi-
niumhydride (DIBAlH) 7,7,7,8,8,8-hexa¯uorosafranal (22)
is obtained. The C3±C4 double bond is selectively removed
by hydrogenation with palladium on charcoal as a catalyst
providing another hexa¯uorinated natural product 7,7,7,
8,8,8-hexa¯uoro-b-cyclocitral (23). Both compounds are
made on a preparative scale and are available for further
synthetic investigations. Especially 23 has the fully func-
tionalized ring system of 16,16,16,17,17,17-hexa¯uororet-
inal and can be used as a starting material for the preparation
of such compounds. For the second time Ð after 2-methyl-
6,6-bis(tri¯uoromethyl)cyclohexanone failed to lead to
hexa¯uororetinals [3] ± there is a good chance to sythesize
the target molecules. Molecular structures and reaction
pathways for the molecules described are shown below.
The crystal structure gave proof of the introduction of a
second double bond in 5,6-position as the distances of
Ê
Ê
The reaction with nucleophilic n-butyl lithium leads to an
addition of the butyl-moiety to the C=C bond but due to
¯uorine abstraction by lithium, the tri¯uoromethyl groups is
de¯uorinated to a CF2-group yielding 1,1-di¯uoro-2-tri-
¯uoromethyl-3-(1,1-di¯uoroethyl)hept-1-ene (16) (see
Scheme 1).
d(C2±C3)ˆ1.35 A and d(C4±C5)ˆ1.33 A are in the range
of C=C bonds in cyclic systems Scheme 2.
3. Experimental
The conversion of 1 with methyl acetoacetate in the
presence of sodium hydride opens a new reaction pathway
for the preparation of molecules which might show some
biological and medical activities. The ®rst step of this
Volatile compounds were handled in a vacuum line.
Solvents were distilled before use and dried according to
published procedures [12]. Melting points (not corrected)
were determined using a Dr. Tottoli apparatus; elemental

K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
119
730 (s), 593 (vvs), 541 (w), 531 (w), 508 (m), 487 (w).
1H NMR (CDCl3) ꢂ: 5.54 (dd, 1H, 2J(H,H)ˆ3.5 Hz,
4J(H,H)ˆ3.5 Hz); 5.86 (dd, 1H, 2J(H,H)ˆ3.5 Hz,
4J(H,H)ˆ3.5 Hz); 6.89 (bs, 1H) ppm. 13C NMR (CDCl3)
ꢂ: 115.17 (t, 1J(C,H)ˆ166.8 Hz); 119.69 (dq, 3J(C,H)ˆ
11.4 Hz, 1J(C,F)ˆ274.6 Hz); 120.69 (q, 1J(C,F)ˆ
274.6 Hz); 122.83 (d, 2J(C,H)ˆ66.7 Hz); 134.03 (d,
1J(C,H)ˆ162.1 Hz); 145.16 (s) ppm. 19F NMR (CDCl3)
ꢂ: 57.04 (q, 4J(F,F)ˆ7.8 Hz); 64.38 (q, 4J(F,F)ˆ7.8 Hz)
(F,F)ˆ7.8 Hz) ppm. 31P NMR (CDCl3) ꢂ: 3.67 (s) ppm. MS,
‡
‡
‡
m/z (%): 326 (M /1), 324 (M /9), 322 (M /14), 287 (1),
285 (8), 283 (11), 269(2), 267 (6), 255 (2), 253 (4), 235 (1),
233 (2), 191 (4), 189 (2), 188 (14), 187 (2), 185 (2), 170 (1),
169 (23), 168 (6), 163 (5), 158 (2), 157 (4), 138 (18), 137 (2),
136 (71), 135 (100), 134 (8), 133 (11), 121 (3), 120 (4), 119
(67), 117 (27), 103 (5), 101 (14), 100 (4), 99 (17), 89 (8), 88
(4), 77 (4), 75 (24), 69 (41), 57 (11), 51 (15), 50 (8), 47 (29).
C6H3Cl2F6O2P (322.91) calculated: C, 22.3; H, 0.9; Cl 21.9.
Found: C, 22.7; H, 1.1; Cl, 18.9.
Scheme 2.
microanalyses were carried out with a Carlo-Erba-Elemen-
tal Analyzer Model 1106. IR spectra were recorded using a
Bruker Vektor 22 and Bruker FT-IR-spectrometer IFS 85;
1H and 19F NMR spectra were recorded with a Bruker WP
80 PFT spectrometer; 13C NMR spectra were obtained
using Bruker WM 250 PFT- and AM 400 PFT-NMR-
spectrometers; 31P NMR spectra were obtained using Bru-
ker WM 250 PFT-NMR spectrometer. As reference stan-
3.1.2. 1,1,1-Trifluoro-2-(trifluoromethyl)-4-
(trimethylsiloxy)penta-2,4-diene (3)
1
dards, TMS was used for H and 13C spectra (internal),
¯uorotrichloromethane for 19F NMR spectra (internal) and
phosphoric acid for 31P spectra (external). Mass spectra of
solids were recorded from electron ionization (EI, 70 eV)
with a Varian MAT-CH 7 instrument; mass spectra of liquids
were obtained with a HP-gaschromatograph 5890 with a
12.5 m capillary column covered with OV1 and an HP MS
Engine 5989 A and electron ionization (EI, 70 eV). X-ray
structural analyses were carried out with a Siemens P4
diffractometer, graphite-monochromated Mo-Ka radiation,
w-Scans. The structures were solved using direct methods
[13] and re®ned against F2o by full-matrix least squares [14].
Hydrogen atoms were placed at calculated positions and
allowed to ride on their parent atoms. Crystallographic data
(excluding structure factors) for the structures reported in
this paper have been deposited with the Cambridge Crystal-
lographic Data Centre.1
0.70 g (6.4 mmol) of trimethylsilylchloride 1.32 g
(6.4 mmol) of 1 and 0.65 g (6.4 mmol) of triethylamine
were condensed in an evacuated 100 ml Carius tube with
Young ventil. After 20 h at RT, 1.75 g (6.2 mmol; 97%) of 3
were isolated by distillation in vacuo (10 3 torr). (b.p.
1478C).
IR (®lm) ꢁ (cm 1): 2967 (m), 1651 (C=C) (s), 1598 (vs),
1426 (w), 1395 (m), 1329 (m), 1282 (m), 1227 (m), 1166
(vvs), 1033 (s), 982 (s), 926 (s), 852 (vvs), 755 (m), 734 (m),
1
695 (w), 644 (m), 605 (w), 537 (w), 517 (m). H NMR
(CDCl3) ꢂ: 0.24 (s, 9H); 4.79 (s, 2H); 6.80 (s,1H) ppm.
1
13C NMR (CDCl3) ꢂ: 0 (q, J(C,H)ˆ118.2 Hz); 106.47 (t,
1J(C,H)ˆ161.1 Hz); 118.89 (m); 118.98 (dq, 3J(C,H)ˆ
13.3 Hz, 1J(C,F)ˆ274.6 Hz); 121.81 (dq, 3J(C,H)ˆ
5.7 Hz, 1J(C,F)ˆ272.7 Hz); 140.20 (d, 1J(C,H)ˆ
148.7 Hz); 150.80 (s) ppm. 19F NMR (CDCl3) ꢂ: 55.52
(q, 4J(F,F)ˆ7.8 Hz); 64.10 (q, 4J(F,F)ˆ7.8 Hz) ppm. MS,
‡
3.1. Syntheses
m/z (%): 278 (18/M ), 209 (14), 186 (4), 168 (6), 167 (82),
158 (11), 146 (12), 139 (59), 120 (3), 119 (8), 117 (2), 113
(2), 101 (4), 89 (6), 81 (6), 79 (6), 78 (8), 77 (100), 75 (18),
74 (6), 73 (63), 72 (6), 71 (2), 69 (8), 65 (6), 64 (11), 59 (2),
57 (4), 51 (5), 49 (18), 47 (12). C9H12F6OSi (278.16): C,
38.8; H, 4.3. Found: C, 38.4; H, 4.0.
3.1.1. 1,1,1-Trifluoro-2-(trifluoromethyl)penta-2,4-dienyl-
dichlorophosphoroacid ester (2)
1.48 g (9.6 mmol) phosphoryl chloride, 1.98 g
(9.6 mmol) of 1 and 0.97 g (9.6 mmol) triethylamine were
condensed in an evacuated 100 ml Carius tube with Young
ventil. After 20 h at RT, 2.33 g (7.2 mmol; 75%) of 2 were
isolated by distillation in vacuo (10 3 torr). (b.p. 1278C,
77 torr).
R (®lm) ꢁ (cm 1): 3136 (w), 3058 (m), 2362 (w), 1664
(C=C) (m), 1605 (s), 1398 (m), 1371 (m), 1275 (m), 1226
(m), 1168(vvs), 1022 (s), 985 (m), 936 (s), 805 (w), 758 (w),
3.1.3. Dimethyl-bis-(1,1,1-trifluoro-2-
trifluoromethylpenta-2,4-dienyl-4-oxysilane (4)
0.70 g (5.4 mmol) of dimethylsilyldichloride, 2.22 g
(10.8 mmol) of 1 and 1.09 g (10.8 mmol) of triethylamine
were condensed in an evacuated 100 ml Carius tube with
Young ventil. After 20 h at RT, 2.15 g (4.6 mmol; 85%) of 4
were isolated by distillation in vacuo(10 3 torr). (b.p.
decomposition).
1Copies of the data (deposition numbers CCDC-) may be obtained free
of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (fax: ‡44-1223/336-033; e-mail: deposit@ccdc.cam.ac.uk).
IR (®lm) ꢁ (cm 1): 2978 (w), 1653 (m), 1599 (m), 1396
(m), 1326 (s), 1282 (s), 1227 (s), 1164 (s), 1037 (m), 983

120
K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
(m), 930 (s), 845 (m), 726 (w), 671 (w), 635 (w), 515 (w),
1
data) for 235 re®ned parameters, Sˆ0.808, Áꢆmaxˆ
Ê Ê
481 (w). H NMR (CDCl3) ꢂ: 0.58 (s, 6H); 5.02 (s, 4H);
0.55 e A 3, Áꢆminˆ 0.50 e A 3, CCDC Nr. 410331.
6.82 (s, 2H) ppm. 13C NMR (CDCl3) ꢂ: 1.58 (q, 1J(C,H)ˆ
122.0 Hz); 108.71 (t, 1J(C,H)ˆ162.1 Hz); 119.36 (m);
120.33 (q, 1J(C,F)ˆ274.6 Hz); 121.57 (q, 1J(C,F)ˆ
267.0 Hz); 138.92 (d, 1J(C,H)ˆ158.3 Hz); 149.29 (s);
3.1.5. 1,1,1-Trifluoro-2-(trifluoromethyl)-4-(p-toluene-
sulfonylhydrazone)pent-2-ene (6a)
To a solution of 8.00 g (38.8 mmol) of 1 and 7.22 g
(38.8 mmol) of p-toluene-sulfonylhydrazine in acetonitrile
(100 ml) placed in a 250 ml ¯ask was added 2 ml concen-
trated hydrochloric acid. After 20 h at RT the solvent was
removed in vacuo and 14.22 g (38.0 mmol; 98%) of 6a was
obtained. (m.p. 1468C).
4
149.29 (s) ppm. 19F NMR (CDCl3) ꢂ: 55.39 (q, J(F,F)
4
ˆ7.8 Hz); 64.20 (q, J(F,F)ˆ7.8 Hz) ppm. MS, m/z (%):
‡
468 (2/M ), 449 (1), 402 (1), 373 (1), 353 (2), 352 (2), 333
(2), 305 (8), 283 (5), 277 (13), 265 (2), 257 (8), 238 (6), 215
(15), 189 (21), 181 (32), 167 (48), 165 (7), 163 (6), 157 (4),
145 (12), 140 (39), 135 (13), 119 (14), 100 (4), 88 (8), 83
(29), 79 (13), 78 (8), 77 (100), 75 (21), 69 (15), 50 (8). 49
(16), 47 (12). C14H12F12O2Si (468.20) calculated: C, 35.8;
H, 2.5. Found: C, 33.3; H, 2.7.
IR (KBr-pellet) ꢁ (cm 1): 3233 (N±H) (w), 1683 (w),
1598 (w), 1395 (w), 1344 (w), 1298 (w), 1217 (w), 1160
(m), 1073 (w), 967 (w), 906 (w), 921 (w), 906 (w), 858 (m),
816 (m), 722 (m), 705 (w), 674 (m), 611 (w), 550 (m), 508
(w), 437 (w). 1H NMR (CDCl3) ꢂ: 1.98 (s, 3H); 1.98 (s, 3H);
3
3.1.4. 1,1,1-Trifluoro-2-(trifluoromethyl)-3-(p-toluene-
sulfonylhydrazine)-pent-4-one (5)
7.01 (s, 1H); 7.32 (d, 2H, J(H,H)ˆ8.2 Hz); 7.82 (d, 2H,
3J(H,H)ˆ8.2 Hz); 8.47 (s, 1H) ppm. 13C NMR (CDCl3) ꢂ:
To a solution of 2.00 g (9.7 mmol) of 1 and 1.8 g
(9.7 mmol) of p-toluene-sulfonylhydrazine in acetonitrile
(20 ml) placed in a 50 ml ¯ask were added 0.25 ml triethy-
lamine. After 20 h at RT the solvent was removed in vacuo
(10 3 torr) and 3.72 g (9.5 mmol; 98%) 5 was obtained.
(m.p. 1358C).
16.52
(q, 1J(C,H)ˆ129.7 Hz);
21.51
(q, 1J(C,H)ˆ
127.7 Hz); 128.79 (d, 1J(C,H)ˆ165.9 Hz); 130.38 (d,
1J(C,H)ˆ156.4 Hz); 136.60 (s); 143.15 (d,1J(C,H)ˆ
165.93); 145.51 (s); 148.45 (s) ppm. 19F NMR (CDCl3)
ꢂ: 58.11 (q, 4J(F,F)ˆ7.8 Hz); 64.04 (dq, 4J(F,H)ˆ
‡
4
1.4 Hz, J(F,F)ˆ7.8 Hz) ppm. MS, m/z (%): 374 (M /6),
278 (1), 242 (2), 199 (17), 190 (15), 158 (3), 157 (33), 156
(9), 155 (30), 140 (7), 139 (22), 121 (18), 101 (12), 93 (9), 92
(39), 91 (100), 77 (8), 69 (17), 65, (38), 63 (9), 58 (2), 57 (3),
52 (3), 51 (12), 41 (5), 39 (20), 29 (5), 28 (8), 27 (4).
C13H12F6N2O2S (374.31) calculated: C, 41.7; H, 3.2; N, 7.4;
S, 8.5. Found: C, 41.9; H, 3.4; N, 7.7; S, 8.3.
IR (KBr-pellet) ꢁ (cm 1): 3278 (w), 3231 (N±H) (w),
1716 (C=O) (w), 1600 (w), 1373 (w), 1335 (w), 1292 (w),
1259 (w), 1224 (w), 1184 (w), 1164 (w), 1088 (w), 872 (w),
811 (w), 725 (w), 697 (w), 667 (w), 550 (w), 533 (w), 487
1
(w) H NMR (CDCl3) ꢂ: 2.23 (s, 3H); 2.37 (s, 3H); 3.57
3
3
(dspt, 1H, J(H,H)ˆ3.0 Hz, J(F,H)ˆ7.8 Hz); 6.20 (d, 1H,
1
3J(H,H)ˆ3.0 Hz); 7.27 (d, 2H, J(H,H)ˆ8.0 Hz); 7.70 (d,
Crystal data: C13H12F6N2O2S, Mˆ374.31, triclinic,
2H, 1J(H,H)ˆ8.5 Hz) ppm. 13C NMR (CDCl3) ꢂ: 21.97 (q,
1J(C,H)ˆ128.7 Hz); 27.47 (q, 1J(C,H)ˆ128.7 Hz); 49.25
(dspt, 1J(C,H)ˆ125.0 Hz, 2J(C,F)ˆ23.9 Hz); 67.14 (d,
1J(C,H)ˆ141.5 Hz); 128.72 (d, 1J(C,H)ˆ147.0 Hz);
129.39 (q, 1J(C,F)ˆ307.0 Hz); 130.12 (d, 1J(C,H)ˆ
136.0 Hz); 134.38 (s); 144.98 (s); 203.12 (s) ppm.
space group P1, aˆ7.105(3), bˆ8.447(3), cˆ
ꢀ
Ê
14.215(5) A, ꢇˆ84.63(3), ꢃˆ88.35(3), ꢈˆ69.27(3)8, Uˆ
Ê 3
794.4(5) A , Zˆ2, F(000)ˆ380, Dcˆ1.565 Mg m 3, ꢄ(Mo-
Ka)ˆ0.277 mm 1. Colorless tablet (0.76Â0.25 Â0.22 mm),
2767 unique re¯ections (2ꢀmaxˆ508) of which 1893 had
Iꢀ2ꢅ(I). Terminal reliability indices were R1ˆ0.078
[Iꢀ2ꢅ(I)], wR2ˆ0.240 (all data) for 235 re®ned parameters,
19F NMR (CDCl3) ꢂ:
62.11 (dq, 3J(F,H)ˆ7.8 Hz,
3
3
4J(F,F)ˆ7.8 Hz); 64.33 (dq, 3J(F,H)ˆ7.8 Hz, 4J(F,F)ˆ
Sˆ0.993, Áꢆmaxˆ0.497 e A
,
Áꢆminˆ 0.471 e A
,
Ê
Ê
‡
7.8 Hz) ppm. MS, m/z (%): 392 (M /1), 351 (1), 350 (3),
CCDC Nr. 410329.
349 (21), 278 (6), 246 (3), 237 (9), 195 (16), 193 (4), 172 (4),
171 (10), 159 (2), 158 (3), 157 (30), 156 (9), 155 (30), 150
(8), 141 (9), 140 (7), 139 (53), 134 (5), 133 (11), 131 (6), 129
(3), 108 (11), 107 (10), 93 (9), 92 (31), 91 (81), 89 (10), 86
(39), 79 (9), 78 (4), 77 (16), 65 (47), 59 (8), 58 (17), 51 (13),
45 (13), 44 (23), 43 (100), 42 (12), 41 (11), 40 (27), 30 (20),
29 (19), 28 (38), 27 (17). C13H14F6N2O3S (392.16) calcu-
lated: C, 39.7; H, 3.5; N, 7.1; S, 8.1. Found: C, 40.7; H, 3.8;
N, 7.7; S, 8.9.
3.1.6. 1,1,1-Trifluoro-2-(trifluoromethyl)-4-(20,40,60-
triisopropylbenzenesulfonylhydrazone)pent-
2-ene (6b)
To a solution of 8.00 g (38.8 mmol) of 1 and 11.7 g
(38.8 mmol) of 2,4,6-triisopropylbenzenesulfonylhydrazine
in acetonitrile (100 ml) placed in a 250 ml ¯ask was added
2 ml concentrated hydrochloric acid. After 20 h at RT the
solvent was removed and 14.22 g (38.0 mmol; 98%) of 6b
was obtained. (m.p. 778C).
Crystal data: C13H14F6N2O3S, Mˆ392.32, monoclinic,
space group P21/n, aˆ15.134(4), bˆ5.184(2), cˆ21.537(6)
IR (KBr-pellet) ꢁ (cm 1): 3256 (N±H) (w), 2964 (w),
2120 (w), 1684 (w), 1601 (w), 1385 (m), 1306 (w), 1212
(w), 1165 (w), 1098 (w), 908 (w), 857 (w), 723 (w), 667 (m),
Ê
Ê 3
A, ꢃˆ99.173(7), Uˆ1668.0(10) A , Zˆ4, F(000)ˆ800,
Dcˆ1.562 Mg m 3, ꢄ(Mo-Ka)ˆ0.272 mm 1. Colorless
tablet (0.56Â0.26Â0.11 mm), 2167 unique re¯ections
(2ꢀmaxˆ558) of which 1007 had Iꢀ2ꢅ(I). Terminal relia-
bility indices were R1ˆ0.063 [Iꢀ2ꢅ(I)], wR2ˆ0.176 (all
1
591 (w), 513 (w), 457 (w). H NMR (CDCl3) ꢂ: 1.23 (d,
18H, 3J(H,H)ˆ6.7 Hz); 1.99 (s, 3H); 2.90 (spt, 2H,
3J(H,H)ˆ6.7 Hz); 4.18 (spt, 1H, 3J(H,H)ˆ6.7 Hz); 6.96

K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
121
‡
(s, 1H); 7.17 (s, 2H); 8.67 (s, 1H) ppm. 13C NMR (CDCl3) ꢂ:
MS, m/z (%): 218 (M /1), 191 (3), 190 (59), 189 (3),
172 (1), 171 (2), 169 (9), 163 (1), 157 (1), 156 (2), 152
(1), 151 (22), 150 (6), 145 (7), 140 (7), 139 (11), 137 (3), 126
(4), 125 (4), 122 (4), 121 (78), 120 (5), 119 (12), 113 (2), 112
(1), 102 (9), 101 (100), 99 (7), 96 (1), 95 (13), 94 (2), 93 (3),
90 (7), 89 (3), 88 (3), 81 (3), 80 (2), 78 (5), 77 (10), 76 (5), 75
(39), 71 (9), 70 (8), 69 (71), 59 (6), 58 (5), 57 (16), 53 (1), 52
(10), 51 (17), 50 (17), 49 (3). C6H4F6N2 (218.06) calculated:
C, 33.0; H, 1.8; N, 12.8. Found: C, 33.2; H, 2.1; N, 12.7.
14.74
(q, 1J(C,H)ˆ129.7 Hz);
23.35
(q, 1J(C,H)ˆ
127.8 Hz); 23.35 (q, 1J(C,H)ˆ127.8 Hz); 24.50 (q,
1
1J(C,H)ˆ127.8 Hz); 29.78 (d, J(C,H)ˆ127.8 Hz); 34.14
(d, 1J(C,H)ˆ133.5 Hz); 123.84 (d, 1J(C,H)ˆ156.4); 130.24
(s); 140.67 (d, 1J(C,H)ˆ158.3); 143.94 (s); 151.43 (s);
153.95 (s) ppm. 19F NMR (CDCl3) ꢂ:
57.93 (q,
4J(F,F)ˆ7.8 Hz); 64.51 (q, 4J(F,F)ˆ7.8 Hz). MS, m/z
(%): 283 (17), 282 (6), 269 (7), 267 (20), 267 (100), 266
(50), 251 (15), 249 (6), 232 (4), 218 (9), 204 (5), 203 (14),
202 (12), 191 (4), 190 (4), 189 (11), 188 (6), 187 (26), 175
(19), 173 (7), 161 (10), 160 (5), 159 (14), 149 (9), 145 (12),
132 (8), 130 (9), 129 (10), 128 (12), 119 (14), 117 (14), 115
(11), 104 (14), 90 (27), 77 (8), 69 (6), 65 (6), 64 (5), 60 (12),
52 (5), 44 (95), 42 (32), 28 (27). C21H29F6N2O2S (487.52)
calculated: C, 51.8; H, 5.7; N, 5.7; S, 6.5. Found: C, 52.2; H,
6.1; N, 5.8; S, 7.0.
3.1.9. 5,5,5-Trifluoro-2-nitro-4-trifluoromethyl-2-(4-
toluenesulfonyl)-pent-3-ene (9)
To 2.00 g (5.3 mmol) of 6a placed in a evacuated 100 ml
Carius tube with Young ventil were added 0.73 g
(15.8 mmol) nitrogen dioxide. After 20 h at RT all volatile
reaction products were removed in vacuo (10 3 torr). The
remaining product was puri®ed by recrystallization from
tetrachloromethane. 0.90 g (2.3 mmol; 43%) of 9 was
obtained. (m.p. 848C).
Crystal data: C21H29F6N2O2S, Mˆ487.52, triclinic,
ꢀ
space group P1, aˆ7.255(2), bˆ12.894(5), cˆ
Ê
13.196(5) A, ꢇˆ74.66(2), ꢃˆ82.07(2), ꢈˆ84.99(2)8,
IR (KBr-pellet) ꢁ (cm 1): 3441 (w), 2368 (w), 1683
(C=C) (w), 1596 (w), 1565 (N=O) (w), 1449 (w), 1416
(w), 1384 (w), 1340 (w), 1299 (w), 1263 (w), 1197 (w),
1159 (w), 1077 (w), 1040 (w), 1016 (w), 985 (w), 941 (w),
896 (w), 850 (w), 821 (w), 810 (w), 716 (w), 704 (w), 682
(w), 668 (w), 621 (w), 591 (w), 577 (w), 558 (w), 543 (w),
3
Ê 3
Uˆ1177.4(7) A , Zˆ2, F(000)ˆ510, Dc 1.375 Mg m
,
1
ꢄ(Mo-Ka)ˆ0.205 mm
.
Colorless tablet (0.7Â0.5
Â0.7 mm), 3041 unique re¯ections (2ꢀmaxˆ458) of which
2281 had Iꢀ2ꢅ(I). Terminal reliability indices were
R1ˆ0.051 [Iꢀ2ꢅ(I)], wR2ˆ0.131 [all data] for 284 re®ned
3
1
Ê
parameters, Sˆ0.908, Áꢆmaxˆ0.350 e A
,
Áꢆmin
ˆ
517 (w), 501 (w), 480 (w), 472 (w). H NMR (CDCl3) ꢂ:
3
3
0.496 e A CCDC Nr. 104485.
Ê
2.17 (s, 3H); 2.50 (s, 3H); 7.32 (s, 1H); 7.41 (d, 2H, J
(H,H)ˆ8.5 Hz); 7.71 (d, 2H, 3J (H,H)ˆ8.5 Hz) ppm.
13C NMR (CDCl3) ꢂ: 21.43 (q, 1J(C,H)ˆ125.8 Hz);
21.90 (q, 1J(C,H)ˆ126.8 Hz); 105.52 (m); 127.14 (q,
3.1.7. 1,1,1-Trifluoro-2-(trifluoromethyl)-4-iodopenta-2,4-
diene (7)
To a solution of 1.00 g (2.7 mmol) of 6a and 0.68 g
(2.7 mmol) iodine in diethylether (10 ml) placed in a
20 ml ¯ask was added 0.27 g (2.7 mmol) triethylamine. 7
could only be characterized by GC-MS analysis. MS, m/z
1J(C,F)ˆ268.9 Hz);
130.38
(d, 1J(C,H)ˆ160.2 Hz);
131.50 (q, 1J(C,F)ˆ268.9 Hz); 132.02 (d, 1J(C,H)ˆ
167.8 Hz); 136.36 (d, 1J(C,H)ˆ164.03 Hz); 139.51 (s);
143.94 (s); 150.06 (s) ppm. 19F NMR (CDCl3) ꢂ: 60.12
‡
(%): 316 (M /93), 190 (5), 189 (100), 169 (40), 167 (32),
139 (19), 127 (22), 120 (6), 119 (26), 101 (13), 99 (14), 77
(10), 75 (18), 70 (6), 69 (29), 58 (13), 50 (21).
(q, 4J(F,F)ˆ7.8 Hz);
64.60 (dq, 4J(F,H)ˆ1.2 Hz,
4J(F,F)ˆ7.8 Hz) ppm. MS, m/z (%): 157 (5), 156 (8),
155 (90), 139 (14), 121 (4), 92 (10), 91 (100), 65 (21),
51 (4), 49 (9), 30 (6). C13H11F6NO4S (391.15) calculated: C,
39.8; H, 2.8; N, 3.5; S, 8.2. Found: C, 39.6; H, 2.8; N, 3.3; S,
8.3.
3.1.8. 5-Methyl-3,3-bis-(trifluoromethyl)-3H-pyrazole (8)
To a solution of 5.00 g (13.3 mmol) of 6a in diethyl ether
(50 ml) placed in a 250 ml ¯ask was added 50 ml of a
sodium carbonate solution (10%). After seven days at RT
the mixture was extracted twice with diethyl ether. The
combined organic layers were dried (MgSO4). 1.44 g
(6.6 mmol; 50%) of 8 was obtained by distillation. (b.p.
1218C).
Crystal data: C13H11F6NO4S, Mˆ391.29, monoclinic,
ace group P21/c, aˆ12.153(2), bˆ10.994(2), cˆ
Ê
Ê 3
12.464(3) A, ꢃˆ100.36(2), Uˆ1637.3(6) A , Zˆ4, F(000)
ˆ 792, Dcˆ1.587 Mg m 3, ꢄ(Mo-Ka)ˆ 0.280 mm 1. Col-
orless tablet (0.66Â0.42Â0.26 mm), 2856 unique re¯ec-
tions (2ꢀmaxˆ508) of which 1564 had Iꢀ2ꢅ(I). Terminal
reliability indices were R1ˆ0.061 (Iꢀ2s(I)), wR2ˆ0.174
IR (®lm) ꢁ (cm 1): 3124 (m), 2967 (w), 1645 (m), 1473
(m), 1443 (m), 1385 (m), 1368 (w), 1308 (w), 1217 (m),
1173 (vs), 1117 (m), 1064 (w), 1008 (w), 979 (s), 931 (w),
912 (m), 844 (m), 801 (m), 753 (m), 737 (m), 721 (s), 650
(all data) for 228 re®ned parameters, Sˆ1.013, Áꢆmax
ˆ
0.441 e A 3, Áꢆminˆ 0.272 e A 3, CCDC Nr. 410330.
Ê
Ê
1
(vvs), 542 (s), 449 (s). H NMR (CDCl3) ꢂ: 2.55 (d, 3H,
3.1.10. 1,1,1-Trifluoro-2-(trifluoromethyl)-5-chloro-pent-
2-en-4-one (10)
To 2.00 g (6.2 mmol) of 2 placed in a 50 ml two-necked
¯ask equipped with a septum and drying tube were added
0.83 g (6.2 mmol) of dimethylamino sulfur tri¯uoride at
408C. The mixture was slowly warmed to RT and stirred
4J(H,H)ˆ1.6 Hz); 6.43 (q, 1H, 4J(H,H)ˆ1.6 Hz) ppm.
13C NMR (CDCl3) ꢂ: 12.92 (q, 1J(CH)ˆ129.7 Hz);
100.91 (dq, 2J(C,H)ˆ9.5 Hz, 2J(C,F)ˆ28.6 Hz); 119.75
(q, 1J(C,F)ˆ284.1 Hz); 121.56 (d, 1J(C,H)ˆ185.0 Hz);
164.02 (s) ppm. 19F NMR (CDCl3) ꢂ: 67.28 (s) ppm.

122
K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
for another 2 h. Then water (10 ml) and diethyl ether
(10 ml) were added. The mixture was extracted twice with
diethyl ether. The combined organic layers were dried
(MgSO4). After removing the solvent in vacuo (10 3 torr)
0.34 g (1.4 mmol; 23%) of 10 was obtained. (b.p. decom-
position).
257 (1), 207 (8), 206 (22), 192 (5), 191 (100), 189 (24), 188
(8), 163 (55), 162 (8), 159 (19), 141 (5), 139 (20), 113 (5), 94
(7), 75 (39), 69 (38), 64 (4), 57 (3), 51 (10). C12H8F12O2
(412.10) calculated: C, 34.9; H, 1.9. Found: C, 34.6; H, 1.9.
3.1.12. 4-Methyl-2,2-bis-(trifluoromethyl)-6-(3,3,3-
trifluoro-2-trifluoromethylpropenyl)-2H-pyran (12)
To 1.00 g (3.6 mmol) of 3 and 0.98 g (7.2 mmol) of zinc
chloride in dichloromethane (20 ml) placed in a 1968C
cooled evacuated 100 ml Carius tube with Young ventil
were condensed 0.72 g (3.8 mmol) titanium tetrachloride.
The mixture was warmed to RT and stirred for 20 h. Then
20 ml of 5% sodium carbonate solution was added. The
organic layer was dried (MgSO4). The volatile substances
were removed in vacuo (10 3 torr). The remaining product
was puri®ed by column chromatography. (Si60; 63±
200 mm; eluent: petroleum ether 40±60/chloroform 20:1).
0.58 g (1.4 mmol; 78%) of 12 was obtained. (b.p. decom-
position).
IR (®lm) ꢁ (cm 1): 3029 (m), 2944 (w), 1808 (w), 1729
(C=O) (s), 1676 (C=C) (w), 1383 (m), 1285 (m), 1222 (w),
1176 (vvs), 1044 (w), 1013 (w), 991 (s), 905 (m), 836 (w),
786 (m), 717 (m), 702 (w), 650 (m), 530 (w), 478 (m).
4
1H NMR (CDCl3) ꢂ: 4.22 (s, 2H); 7.16 (q, 1H, J(H,F)ˆ
1.1 Hz) ppm. 13C NMR (CDCl3) ꢂ: 47.16 (t, 1J(C,H)ˆ
152.5 Hz); 119.83 (q, 1J(C,F)ˆ276.5 Hz); 119.55 (q,
1J(C,F)ˆ276.5Hz); 126.42 (m); 138.16 (d, 1J(C,H)ˆ
167.8 Hz); 191.59 (s) ppm. 19F NMR (CDCl3) ꢂ: 60.72
(q, 4J(F,F)ˆ7.8 Hz);
65.52 (dq, 4J(C,H)ˆ1.1 Hz,
‡
4J(F,F)ˆ7.8 Hz) ppm. MS, m/z (%): 240 (M /1), 212 (1),
195 (2), 193 (6), 192 (6), 191 (100), 174 (2), 173 (10), 172
(1), 170 (6), 164 (2), 163 (48), 157 (12), 144 (1), 142 (2), 140
(4), 137 (4), 121 (2), 113 (4), 95 (2), 94 (2), 93 (4), 77 (4), 76
(3), 75 (48), 69 (51), 57 (3), 56 (4), 53 (3), 51 (18), 49 (27),
48 (3). C6H3ClF6O (240.50) calculated: C, 29.9; H, 1.2; Cl,
14.7. Found: C, 29.8; H, 1.1; Cl, 13.1.
IR (®lm) ꢁ (cm 1): 3093 (w), 2994 (w), 2931 (m), 2866
(w), 1676 (m), 1639 (C=C) (vvs), 1579 (m), 1454 (w), 1442
(m), 1411 (s), 1388 (m), 1172 (vvs), 1078 (s), 975 (vs), 954
(w), 921 (s), 843 (m), 826 (w), 795 (vs), 749 (vs), 726 (m),
714 (vs), 664 (s), 646 (m), 583 (w), 567 (w), 554 (w), 534
1
3.1.11. 1,1,1,9,9,9-Hexafluoro-6-hydroxy-6-methyl-2,8-
bis(trifluoromethyl)nona-2,7-dien-4-one (11)
(w), 525 (m), 488 (m). H NMR (CDCl3) ꢂ: 1.95 (s, 3H);
5.33 (s, 1H); 5.68 (s, 1H); 6.65 (s, 1H) ppm. 13C NMR
To 1.00 g (3.6 mmol) of 3 and 0.98 g (7.2 mmol) of zinc
chloride in dichloromethane (20 ml) placed in a 1968C
cooled evacuated 100 ml Carius tube with Young ventil
were condensed 0.72 g (3.8 mmol) titanium tetrachloride.
The mixture was warmed to 788C and stirred for 20 h.
Then 20 ml of sodium carbonate solution (5%) were added.
The organic layer was dried (MgSO4). The volatile sub-
stances were removed in vacuo (10 3 torr). The remaining
product was puri®ed by column chromatography. (Si60; 63±
200 mm; eluent: petroleum ether 40±60/chloroform 20:1).
0.58 g (1.4 mmol; 78%) of 11 was obtained. (b.p. decom-
position).
(CDCl3) ꢂ: 20.37 (q, 1J(C,H)ˆ128.7 Hz); 80.91 (dspt,
2
1
2J(C,H)ˆ7.3 Hz, J(C,F)ˆ33.1 Hz); 106.38 (d, J(C,H)ˆ
172.81 Hz); 114.38 (d, 1J(C,H)ˆ167.29 Hz); 120.11 (q,
1J(C,F)ˆ273.9 Hz); 120.15 (spt, 2J(C,F)ˆ31.2 Hz);
120.23 (q, 1J(C,F)ˆ273.9 Hz); 121.27 (q, 1J(C,F)ˆ
288.6 Hz); 132.38 (d, 1J(C,H)ˆ167.1 Hz); 136.96 (s);
145.16 (s) ppm. 19F NMR (CDCl3) ꢂ:
56.94 (q,
4J(F,F)ˆ7.8 Hz); 64.30 (q, J(F,F)ˆ7.8 Hz); 78.90 (s)
4
‡
ppm. MS, m/z (%): 394 (M /14), 374 (12), 373 (7), 354 (3),
347 (3), 346 (2), 327 (3), 326 (13), 325 (100), 307 (4), 306
(3), 305 (10), 287 (3), 285 (7), 277 (7), 257 (13), 236 (7), 230
(5), 227 (3), 220 (3), 192 (3), 191 (49), 178 (13), 169 (5), 163
(38), 145 (10), 132 (6), 113 (6), 112 (7), 101 (3), 99 (3), 95
(8), 75 (24), 73 (10), 69 (42), 51 (15). C12H6F12O (394.11)
calculated: C, 36.5; H, 1.5. Found: C, 36.3; H, 1.7.
IR (®lm) ꢁ (cm 1): 3537 (O±H) (s), 2990 (m), 2360 (m),
1785 (w), 1718 (C=O) (s), 1675 (C=C) (m), 1639 (w), 1262
(s), 995 (m), 904 (m), 855 (w), 826 (w), 775 (w), 719 (m),
1
680 (m), 649 (m), 493 (m). H NMR (CDCl3) ꢂ: 1.45 (s,
3H); 2.95 (d, 1H, 2J (H,H)ˆ18.1 Hz); 3.09 (d, 1H, 2J
3.1.13. 2-(4,4,4-Trifluoro-1-hydroxy-1-methyl-3-
trifluoromethylbut-2-enyl)cyclohexanone (13)
4
(H,H)ˆ18.1 Hz); 6.72 (q, 1H, J(F,H)ˆ0.9 Hz); 6.90 (q,
1H, 3-CH, 4J(F,H)ˆ1.2 Hz) ppm. 13C NMR (CDCl3) ꢂ:
26.96 (q, 1J(C,H)ˆ129.5 Hz); 53.45 (t, 1J(C,H)ˆ
128.8 Hz); 71.07 (s); 120.04 (q, 1J(C,F)ˆ275.9 Hz);
120.17 (q, 1J(C,F)ˆ275.9 Hz); 120.81 (q, 1J(C,F)ˆ
274.3 Hz); 120.95 (q, 1J(C,F)ˆ274.3 Hz); 125.68 (spt,
2J(C,F)ˆ30.7 Hz); 125.72 (spt, 1J (C.F)ˆ30.7 Hz);
139.33 (d, 1J(C,H)ˆ163.4 Hz); 149.98 (d, 1J(C,H)ˆ
157.5 Hz); 197.34 (s) ppm. 19F NMR (CDCl3) ꢂ: 55.76
To 2.00 g (9.7 mmol) of 1, 1.65 g (9.7 mmol) of 1-tri-
methylsiloxycyclohexene and 2.64 g (19.4 mmol) of zinc
chloride in dichloromethane (20 ml) placed in a 1968C
cooled evacuated 100 ml Carius tube with Young ventil,
3.68 g (19.4 mmol) titanium tetrachloride was condensed.
The mixture was warmed to 788C and stirred for 20 h.
Then 20 ml of sodium carbonate solution (5%) was added.
The organic layer was dried (MgSO4). The volatile sub-
stances were removed in vacuo (10 3 torr). The residue was
puri®ed by column chromatography (Si 60; 63±200 mm;
eluent: petroleum ether 40±60/chloroform 20:1). 1.97 g
(6.4 mmol; 67%) of 13 was obtained. (b.p. decomposition).
4
4
(q, J(F,F)ˆ8.0 Hz); 60.35 (q, J(F,F)ˆ6.5 Hz); 64.91
(dq, 4J(F,H)ˆ1.2 Hz, 4J(F,H)ˆ8.0 Hz);
65.65 (dq,
4J(F,H)ˆ0.9 Hz, 4J(F,H)ˆ6.5 Hz) ppm. MS, m/z (%):
‡
412 (M /1), 397 (5), 375 (3), 326 (2), 325 (16), 305 (1),

K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
123
IR (®lm) ꢁ (cm 1): 3519 (m), 2942 (s), 2867 (m), 1701
(s), 1667 (w), 1452 (m), 1403 (m), 1366 (w), 1301 (m), 1236
(m), 1165 (vvs), 1047 (w), 978 (m), 950 (w), 903 (w), 841
(w), 813 (w), 759 (m), 721 (m), 657 (m), 563 (m), 517 (w),
440 (w), 428 (w). 1H NMR (CDCl3) ꢂ: 1.27 (s, 3H); 1.5±2.6
(m, 9H); 6.82 (s, 1H) ppm. 13C NMR (CDCl3) ꢂ: 23.67 (q,
1J(C,H)ˆ126.8 Hz); 24.94 (t, 1J(C,H)ˆ128.7 Hz); 28.10 (t,
1J(C,H)ˆ128.7 Hz); 28.52 (t, 1J(C,H)ˆ130.1 Hz); 42.92 (t,
were distilled in vacuo (10 3 torr) and dried (MgSO4).
2.25 g (9.1 mmol; 45%) 15 was obtained by distillation.
(b.p. 1208C).
IR (®lm) ꢁ (cm 1): 3454 (w), 3380 (w), 3013 (w), 2976
(w), 1738 (w), 1630 (w), 1406 (s), 1391 (s), 1314 (vs), 1279
(vs), 1225 (vs), 1176 (vvs), 1113 (vs), 1006 (w), 897 (s), 821
(w), 735 (w), 713 (w), 638(w), 603 (w), 551 (w), 541 (w),
515 (w), 458 (w). 1H NMR (CDCl3) ꢂ: 1.59 (m); 1.78 (t, 3H,
3J(H,F)ˆ18.8 Hz); 3.48 (m); 3.50 (m). 13C NMR (CDCl3)
ꢂ: 21.17 (tq, 1J(C,H)ˆ129 Hz, 2J(C,F)ˆ27 Hz); 47.37
(ddsep, 1J(C,H)ˆ128 Hz; 2J(C,H)ˆ4 Hz; 2J(C,F)ˆ26 Hz);
(C,F)ˆ26 Hz); 54.11 (dt, 1J(C,H)ˆ136 Hz, 2J(C,F)ˆ
1
1J(C,H)ˆ125.0 Hz); 59.96 (d, J(C,H)ˆ126.85 Hz); 72.66
(s); 120.74 (q, 1J(C,F)ˆ273.9 Hz); 121.43 (q, 1J(C,F)ˆ
272.0 Hz); 124.30 (m); 154.14 (d, 1J(C,H)ˆ156.2 Hz);
4
214.02 (s) ppm. 19F NMR (CDCl3) ꢂ: 55.50 (q, J(F,F)
4
1
1
ˆ7.8 Hz); 64.40 (q, J 4J(F,F)ˆ7.8 Hz) ppm. MS, m/z
27 Hz); 122.63 (t, J(C,F)ˆ245 Hz); 122.91 (q, J(C,F)ˆ
‡
(%): 304 (M /3), 289 (1), 257 (1), 243 (1), 217 (6), 208 (3),
279 Hz); 123.74 (q, 1J(C,F)ˆ280 Hz). 19F NMR (CDCl3) ꢂ:
3
5
4
207 (5), 206 (1), 199 (3), 191 (22), 187 (14), 163 (20), 159
(13), 145 (3), 141 (3), 139 (14), 125 (6), 99 (13), 98 (100), 97
(21), 95 (8), 83 (37), 81 (8), 80 (3), 79 (6), 77 (23), 71 (8), 70
(56), 69 (38), 63 (6), 57 (6), 56 (10), 55 (76), 54 (6), 53 (6),
50 (8). C12H14F6O2 (304.10) calculated: C, 47.3; H, 4.6.
Found: C, 47.3; H, 4.9.
60.58 (ddq, J(F,H)ˆ2.0 Hz, J(F,F)ˆ16.6 Hz, J(F,F)ˆ
9.3 Hz); 67.39 (dq, 3J(F,H)ˆ7.3 Hz, 4J(F,F)ˆ9.3 Hz);
95.84 (ddq,3J(F,H)ˆ3.0 Hz, J(F,F)ˆ247.8 Hz, J(F,H)ˆ
2
3
18.8 Hz);
247.8 Hz, 3J(F,H)ˆ18.8 Hz, 5J(F,F)ˆ16.6 Hz) ppm. MS,
106.13 (ddqq, 3J(F,H)ˆ16.0 Hz, 2J(F,F)ˆ
‡
m/z (%): 246 (M /1), 226 (3), 206 (2), 180 (100), 160 (8),
140 (2), 94 (28), 74 (16), 69 (8), 65 (8). C6Hd7F8N (245.11)
calculated:C,29.3;H,2.8;N,5.7.Found:C,292;H,28;N,6.2.
3.1.14. 1,1,1,4,4-Pentafluoro-2-trifluoromethylpent-2-ene
(14)
To 20.00 g (97 mmol) of 1 and 10 g of anhydrous hydro-
gen ¯uoride placed in a 1968C cooled evacuated 200 ml
autoclave, 16 g (148 mmol) of sulfurtetra¯uoride was con-
densed. The mixture was warmed to 208C and stirred for
18 h. Then the autoclave was cooled to 788C, opened and
150 g ice was added to the reaction mixture. The organic
layer was washed with 20 ml of sodium carbonate solution
(10%) and dried (MgSO4). After distillation 14 g (61 mmol
63%) of 14 was obtained. (b.p. 798C).
3.1.16. 1,1-Difluoro-2-trifluoromethyl-3-(1,1-
difluoroethyl)hept-1-ene (16)
To 5.00 g (22 mmol) of 14 placed in a 788C cooled
50 ml two-necked ¯ask equipped with a septum and drying
tube, 13.7 ml (22 mmol) of a 1.6 M butyllithium solution in
n-hexane was added. The mixture was slowly warmed to
208C. The volatile substances were distilled in vacuo
(10 3 torr) in a 1968C cooled trap and puri®ed by pre-
parative gas chromatography (Perkin-Elmer F 21; stationary
phase OV 17, 1008C). 0.5 g (1.8 mmol; 8%) 16 was
obtained. (b.p. decomposition).
IR (®lm) ꢁ (cm 1): 3049 (w), 1694 (w), 1391 (vs), 1301
(vs), 1265 (vvs), 1218 (vs), 1187 (vvs), 984 (s), 955 (s), 934
(s), 897 (s), 723 (s), 656 (s), 593 (s), 541 (s), 526 (s).
1H NMR (CDCl3) ꢂ: 1.82 (t, 3H, 3J(H,F)ˆ18.1 Hz); 6.71 (t,
1H, 3J(H,F)ˆ12.6 Hz). 13C NMR (CDCl3) ꢂ: 23.87 (tq,
IR (solution in CDCl3 with CDCl3 as reference)
ꢁ (cm 1): 2962 (s), 2932 (s), 2875 (s), 1734 (vvs), 1539
1
(w), 1456 (s), 1138 (vvs), 1033 (s). H NMR (CDCl3) ꢂ:
2
1
1J(C,H)ˆ129 Hz, J(C,F)ˆ28 Hz); 118.06 (tm, J(C,F)ˆ
239 Hz); 119.34 (dq, 1J(C,F)ˆ275 Hz, 3J(C,H)ˆ8 Hz);
120.30 (dq, 1J(C,F)ˆ268 Hz, 3J(C,H)ˆ13 Hz); 126.26
(dm, 2J(C,H)ˆ4 Hz); 139.69 (dt, 1J(C,H)ˆ166 Hz,
0.92 (t, 3H, 3J (H,H)ˆ6.9 Hz); 1.33 (m, 2H); 1.35 (m, 2H),
3
3
1.63 (t, 3H, J(H,F)ˆ18.6 Hz); 1.77 (dt, 2H, J (H,H)ˆ
6.9 Hz, 3J (H,H)ˆ6.9 Hz); 2.78 (m, 1H). 13C NMR (CDCl3)
ꢂ: 13.71 (q, 1J(C,H)ˆ124 Hz); 22.11 (tq, 1J(C,H)ˆ128 Hz,
2J(C,F)ˆ28 Hz); 22.11 (t, 1J(C,H)ˆ124 Hz); 25.20 (t,
2J(C,F)ˆ28 Hz). 19F NMR (CDCl3) ꢂ:
59.03 (tq,
4J(F,F)ˆ7.6 Hz, 5J(F,F)ˆ14.4 Hz); 65.83 (dtq, 4J(F,H)
ˆ7.4 Hz, 4J(F,F)ˆ7.6 Hz, 5J(F,F)ˆ1.5 Hz); 87.30 (dqqq,
3J(F,H)ˆ12.6 Hz, 3J(F,H)ˆ18.1 Hz, 5J(F,F)ˆ1.5 Hz,
5J(F,F)ˆ28 Hz) ppm. MS, m/z (%): 213 (100), 208 (23),
189 (48), 169 (14), 163 (50), 159 (75), 139 (31), 119 (6), 113
(19), 69 (36), 65 (58). C6H4F8 (228.08) calculated: C, 31.5;
H, 1.8. Found: C, 31.8; H, 2.0.
1J(C,H)ˆ129 Hz); 29.24 (t, J(C,H)ˆ124 Hz); 43.52 (dt,
1
2
1J(C,H)ˆ129 Hz, J(C,F)ˆ28 Hz); 85.18 (m); 122.83 (q,
1
1J(C,F)ˆ272 Hz); 123.30 (t, J(C,F)ˆ242 Hz); 157.93 (t,
1J(C,F)ˆ302 Hz). 19F NMR (CDCl3) ꢂ:
59.43 (m);
69.83 (m); 73.05 (m); 93.55 (m) ppm. MS, m/z
‡
(%): 266 (M /1), 246 (3), 201 (5), 181 (82), 159 (98),
145 (58), 115 (7), 113 (19), 95 (12), 69 (12), 65 (100), 57
(65). C10H13F7 (266.19) calculated: C, 45.1; H, 4.8. Found:
C, 45.2; H, 4.9.
3.1.15. 1,1,1,4,4-Pentafluoro-2-trifluoromethyl-3-
aminopentane (15)
To 5.00 g (22 mmol) of 14 and 1.7 g (22 mmol) of sodium
amide placed in a 50 ml Carius tube with Young ventil, 0.8 g
(44 mmol) of water was added. The Carius tube was closed
and heated for 15 min to 1008C. The volatile substances
3.1.17. 4-Acetyl-2-fluoro-6-methyl-5-methoxycarbonyl-3-
trifluoromethylpyran (17)
To 0.98 g (20 mmol) of a sodium hydride suspension
(50%) placed in a 50 ml two-necked ¯ask equipped with a

124
K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
septum and drying tube, 50 ml THF and slowly 1.15 ml
(10 mmol) methyl acetoacetate were added. Then 2.10 g
(10 mmol) of 1 was added and the reaction mixture was
stirred at RT for 20 h. The reaction was stopped by adding
10 ml diluted hydrochloric acid and the mixture the mixture
was extracted twice with diethylether. The combined
organic layers were dried (Na2SO4). The volatile substances
were removed by rotation evaporator. The obtained product
was puri®ed by distillation in vacuo (10 3 torr). 1.68 g
(5.9 mmol; 58%) 17 was obtained. (b.p. 468C, 10 2 torr).
IR (®lm) ꢁ (cm 1): 2959 (s), 1746 (C=O) (vs), 1655 (s),
1438 (s), 1373 (vs), 1248 (vs), 1215 (vs), 1184(vs), 1127
(43), 161 (53), 141 (19), 69 (43), 68 (100), 67 (38), 53 (26).
C10H9F6N (257.18) calculated: C, 46.7; H, 3.5; N, 5.4.
Found: C, 45.8; H, 3.8; N, 5.7.
3.1.19. 1,1-Bis(trifluoromethyl)-5-methyl-6-
cyanocyclohexa-3,5-diene (21)
4.5 g (17.5 mmol) of 20 and 3.6 g (20.2 mmol) of N-
bromosuccinimide were dissolved in 50 ml carbon ter-
achloride and re¯uxed for 3 h. The white succinimide
was ®ltered off and the orange solution was cooled to
08C. 2.5 ml of triethylamine was added and the mixture
was stirred for 1 h at 08C. The reaction was quenched by
15 ml of diluted hydrochloric acid. After 30 min the organic
phase is separated and washed two times with water. The
solvent is removed under reduced pressure and 5.1 g of an
orange oil was obtained. This oil is a complex mixture of
educt, product and some monobromo and dibromo deriva-
tives. 1 ml of petroleum ether 40±60 was added and the
mixture was stored overnight at 188C. Now the solids 20
and 21 were ®ltered off and puri®ed by sublimation (1008C,
15 mbar) and separated by MPLC (petroleum ether 40±60/
chloroform 100:1). Pure 20 (1.39 g, 5.4 mmol, 31%) and 21
(1.42 g, 5.6 mmol, 32%, 63% of conversation) were
obtained. 21 is a white solid melting at 788C.
1
(vs), 1079 (vs), 1014 (vs), 772 (w). H NMR (CDCl3) ꢂ:
2.23 (s, 3H), 2.31 (s, 3H), 3.76 (s, 3H), 4.34 (d, 1H,
4J(H,F)ˆ6.4 Hz). 13C NMR (CDCl3) ꢂ: 18.02 (q,
1
1J(C,H)ˆ129.7 Hz), 28.60 (q, J(C,H)ˆ127.8 Hz), 45.04
(d, 1J(C,H)ˆ141.1 Hz), 52.04 (q, 1J(C,H)ˆ146.9 Hz),
2
2
2
81.00 (ddq, J (C;F)ˆ36.2 Hz, J(C,F)ˆ13.4 Hz, J(C,H)
ˆ7.63 Hz), 105.47 (s), 122.59 (q, 1J(C,F)ˆ273.2 Hz),
155.08 (d, 1J(C,F)ˆ271.1 Hz), 160.21 (s), 165.15 (s),
205.85 (s). 19F NMR (CDCl3) ꢂ: 60.17 (d, 4J(F,F)ˆ
4
4
20.3 Hz), 86.21 (qd, J(F,F)ˆ20.3 Hz, J(F,H)ˆ6.4 Hz)
‡
ppm. MS, m/z (%): 282 (M /1), 251 (11), 239 (100), 219
(49), 207 (10), 199 (17), 191 (13), 163 (21), 161 (8), 151 (7),
132 (7), 113 (6), 101 (8), 83 (14), 69 (4), 63 (4), 59 (44).
C11H10F4O4 (282.19) calculated: C, 46.8; H, 3.6. Found: C,
45.7; H, 3.7.
IR (KBr-pellet) ꢁ (cm 1): 2214 (CN) (w), 1651 (w), 1579
(w), 1437 (w), 1282 (vs), 1226 (vs), 1152 (s), 1008 (s), 988
(s), 972 (s), 960 (w), 878 (w), 835 (w), 779 (s), 735 (w), 719
(vw), 703 (vw), 529 (vw). 1H NMR (CDCl3) ꢂ: 2.23 (s, 3H),
2.83 (d, 2H, 3J (H,H)ˆ2.7 Hz), 6.05±6.20 (m, 2H).
13C NMR (CDCl3) ꢂ: 24.19 (q, 1J(C,H)ˆ129.7 Hz),
51.02 (sep, 2J(C,F)ˆ31.2 Hz), 94.07 (s), 115.48 (s),
124.00 (q, 1J(C,F)ˆ286.1 Hz), 125.65 (d, 1J(C,H)ˆ
162.1 Hz), 129.49 (d, 1J(C,H)ˆ167.8 Hz), 155.78 (s).
19F NMR (CDCl3) ꢂ: 71.96 (s) ppm. MS, m/z (%):
3.1.18. (5-R,6-S/5-S,6-R)-1,1-bis(trifluoromethyl)-5-
methyl-6-cyanocyclohex-3-ene (20)
15.0 g (53.2 mmol) of 1,1-bis(tri¯uoromethyl)-5-methyl-
6,6-dicyano-cyclohex-3-en (19) was dissolved in 30 ml
ethanol and cooled to 08C. A solution of 10.0 g (250 mmol)
sodium hydroxide in 15 ml water was slowly added. The
yellow mixture was stirred for ®ve days at 228C, forming
slowly a white precipitate. The precipitate was ®ltered off
and washed with water. The crude product was puri®ed by
sublimation (1008C, 15 mbar). Pure 20 (13.26 g,
51.6 mmol; 97.0%) was obtained as a white solid melting
at 938C.
‡
255(M /37), 240 (1), 234 (1), 186 (100), 184 (11), 166
(75), 152 (4), 116 (13), 69 (43), 51 (7).
3.1.20. 1,1-Bis(trifluoromethyl)-6-formyl-5-methyl-
cyclohexa-3,5-diene or 7,7,7,8,8,8-
hexafluorosafranal (22)
IR (KBr-pellet) ꢁ (cm 1): 2982 (w), 2247 (CN) (s), 1463
(w), 1369 (w), 1277 (s), 1223 (s), 1200 (vs), 1188 (vs), 1160
(s), 1127 (s), 1095 (s), 1072 (s), 1058 (s), 993 (w), 972 (w),
935 (w), 874 (w), 856 (w), 801 (w), 718 (s), 697 (s), 669 (w).
0.5 g (1.96 mmol) of 21 was dissolved in 5 ml n-hexane at
358C in an argon atmosphere. 29 ml (29 mmol, 15 equiva-
lents) of a 1 M solution of diisobutylaluminiumhydride was
added via syringe and stirred for 6 h at 358C. The reaction
was quenched by addition of 5 ml ethyl acetate. After warm
up to 08C 15 ml diethylether and 20 ml diluted sulfuric acid
were added and stirred for another 30 min. The organic
phase was separated and washed two times with brine. The
solvents were removed under reduced pressure and the
crude yellow liquid was puri®ed by chromatography (pet-
roleum ether 40±60/ethyl acetate 100:1). 22 (354 mg,
1.37 mol, 70%) was obtained as a colorless liquid boiling
at 998C/15 torr.
3
1H NMR (CDCl3) ꢂ: 1.30 (d, 3H, J (H,H)ˆ6.7 Hz), 2.41
(d, 1H, 2J (H,H)ˆ18.6 Hz), 2.55 (d, 1H, 2J (H,H)ˆ
18.6 Hz), 2.58±2.68 (m, 1H), 2.73 (d, 1H, 2J (H,H)ˆ
11.0), 5.59±5.65 (m, 2H). 13C NMR (CDCl3) ꢂ: 19.54 (q,
1
1J (C;H)ˆ127.8 Hz), 25.54 (t, J(C,H)ˆ131.6 Hz), 31.03
(d, 1J(C,H)ˆ135.4 Hz), 34.36 (d, 1J(C,H)ˆ137.3 Hz),
51.13 (sep, 2J(C,F)ˆ26.7 Hz), 116.48 (d, 2J(C,H)ˆ9.5 Hz),
(C,H)ˆ9.5 Hz), 120.70 (ddd, 1J C,H)ˆ164.0 Hz, 2J(C,H)ˆ
2
1
12.4 Hz, J(C,H)ˆ6.6 Hz), 123.98 (q, J(C,F)ˆ286.1 Hz),
130.34 (d, 1J (C.H)ˆ164.0 Hz). 19F NMR (CDCl3) ꢂ:
IR (®lm) ꢁ (cm 1): 1691 (s), 1651 (w), 1553 (s), 1432 (s),
1305 (w), 1270 (vs), 1193 (vs), 1133 (s), 1011 (s), 733 (s),
4
4
67.98 (q, J(F,F)ˆ9.8 Hz), 71.90 (q, J(F,F)ˆ9.8 Hz)
‡
1
ppm. MS, m/z (%): 257 (M /37), 242 (32), 230 (21), 188
103 (w). H NMR (CDCl3) ꢂ: 2.19 (s, 3H), 2.76 (bs, 2H),

K. Brandt et al. / Journal of Fluorine Chemistry 97 (1999) 115±125
125
5.95 (bs, 2H), 9.79 (s, 1H). 13C NMR (CDCl3) ꢂ: 21.80 (q,
1J(C,H)ˆ124.0 Hz), 26.78 (t, 1J(C,H)ˆ135.4 Hz), 51.74
(sep, 2J(C,F)ˆ26.7 Hz), 102.97 (d, 1J(C,H)ˆ165.9 Hz),
118.33 (d, 2J(C,H)ˆ24.8 Hz), 124.94 (q, 1J(C,F)ˆ
286.1 Hz), 129.61 (td, 1J(C,H)ˆ167.8 Hz, 2J(C,H)ˆ
7.6 Hz), 151.51 (s), 190.18 (d, 1J(C,H)ˆ181.2 Hz).
19F NMR (CDCl3) ꢂ: 69.56 (s) ppm. MS, m/z (%): 258
163 (25), 143 (24), 141 (19), 127 (17), 123 (15), 115 (11), 95
(9), 79 (13), 77 (15), 69 (14), 65 (20), 51 (14), 47 (13).
Acknowledgements
This work is ®nanced by the EU Commission in Brussel.
Project Number ERB FMR-XCT 970120. We are thankful
to Hoechst AG Frankfurt for the generous supply of ¯uori-
nated chemicals.
‡
(M /80), 239 (3), 209 (3), 189 (3), 187 (2), 169 (12), 161
(50), 145 (9), 141 (100), 119 (8), 109 (9), 101 (10), 91 (20),
69 (15), 65 (19), 51 (17).
3.1.21. 1,1-Bis(trifluoromethyl)-6-formyl-5-methyl-
cyclohex-5-ene or 7,7,7,8,8,8-hexa-fluoro-
References
b-cyclocitral (23)
[1] A. Haas, M. Lieb, M. Schelvis, J. Fluorine Chem. 83 (1997) 133±
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0.20 g (0.78 mmol) of 22 was dissolved in 20 ml methy-
lene chloride and 0.20 g of palladium (10%) on charcoal
was added. The mixture was stirred for 20 h in a hydrogen
atmosphere at 228C/1 bar. The charcoal was ®ltered off and
the solvent removed under reduced pressure. The remaining
yellow oil was puri®ed by chromatography (petroleum ether
40±60/acetic acid ethylester 20:1). Pure 23 (0.174 g,
0.67 mmol, 86%) was obtained as a colorless liquid boiling
at 1018C, 15 torr.
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IR (®lm) ꢁ (cm 1): 2977 (s), 1702 (C=O) (vs), 1601 (vs),
1458 (s), 1422 (s), 1379 (s), 1355 (s), 1264(vs), 1206 (vs),
1178 (s), 1148 (s), 1080 (w), 992 (s), 976 (s), 930 (s), 917
[9] F. Bottomley, L. Sutin, Adv. Organomet. Chem. 28 (1988) 339.
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[11] T. Mukaiyama, K. Banno, K. Narasaka, J. Am. Chem. Soc. 96 (1974)
7506±7509.
1
(s), 734 (s), 718 (w). H NMR (CDCl3) ꢂ: 1.54±2.34 (m,
6H), 2.09 (s, 3H). 13C NMR (CDCl3) ꢂ: 16.84 (t,
1J(C,H)ˆ127.8 Hz), 23.53 (q, J(C,H)ˆ128.1 Hz), 25.30
1
[12] H. Henda, in: E. MuÈller (Ed.), Methoden Org. Chem. (Houben-
Weyl), vol. I/2, Thieme, Stuttgart, 1959, p. 765; Organikum, VEB
Deutscher Verlag der Wissenschaften, Berlin, 1977, p. 321.
[13] G.M. Sheldrick, SHELXS-86, Acta Crystallogr. A 46 (1990) 467.
(t, 1J(C,H)ˆ137.3 Hz), 33.56 (t, 1J(C,H)ˆ124.0 Hz), 51.95
(m), 123.02 (d, 2J(C,H)ˆ17.2 Hz), 124.83 (q, 1J(C,F)ˆ
288.0 Hz), 160.24 (s), 191.53 (d, 1J(C,H)ˆ179.3 Hz).
19F NMR (CDCl3) ꢂ: 67.39 (s) ppm. MS, m/z (%): 260
È È
[14] G.M. Sheldrick, SHELXL-93, Universitat Gottingen, 1993.
[15] W.J. Middleton, J. Org. Chem. 30 (1965) 1402±1407.
[16] R. Huisgen, R. BruÈckner, Tetrahedron Lett. 35 (1994) 3285±3288.
‡
(M /100), 245 (19), 231 (18), 225 (16), 191 (19), 171 (30),