Synthesis and molecular and crystalline structure of polyfluoro-1,3- diazafluorenes

Article abstract of DOI:10.1023/B:RUJO.0000034983.96937.18

Reactions of 2-amino-3-(1-imino-2,2,2-trifluoroethyl)hexafluoro-1H-indene with carboxylic acid anhydrides and chlorides afforded 2-alkyl(aryl)-4- trifluoromethyl-5,6,7,8,9,9-hexafluoro-1,3-diazafluorenes. The molecular and crystalline structure of the pro

Full text of DOI:10.1023/B:RUJO.0000034983.96937.18

Russian Journal of Organic Chemistry, Vol. 40, No. 3, 2004, pp. 421–425. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 3, 2004,
pp. 448–452.
Original Russian Text Copyright © 2004 by Karpov, Platonov, Chuikov, Rybalova, Gatilov, Shakirov.
Synthesis and Molecular and Crystalline Structure
of Polyfluoro-1,3-Diazafluorenes
V. M. Karpov, V. E. Platonov, I. P. Chuikov, T. V. Rybalova,
Yu. V. Gatilov, and M. M. Shakirov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: karpov@nioch.nsc.ru
Received May 28, 2003
Abstract—Reactions of 2-amino-3-(1-imino-2,2,2-trifluoroethyl)hexafluoro-1H-indene with carboxylic acid
anhydrides and chlorides afforded 2-alkyl(aryl)-4-trifluoromethyl-5,6,7,8,9,9-hexafluoro-1,3-diazafluorenes.
The molecular and crystalline structure of the products was studied by NMR spectroscopy and X-ray
diffraction. 5,6,7,8,9,9-Hexafluoro-2-phenyl-4-trifluoromethyl-1,3-diazafluorene in crystal gives rise to infinite
ladder chains via π-stacking interaction between the benzene ring of one molecule and tetrafluorobenzene
fragment of the other.
We recently synthesized first fluorine-containing
derivatives of dihydro-2-selena-1,3-diazafluorene from
2-amino-3-(1-imino-2,2,2-trifluoroethyl)hexafluoro-
indene (I) and SeCl4. These compounds are
representatives of a new polyfluoro-2-elementa-1,3-
diazafluorene series [1]. Intramolecular cyclization of
2-dialkylamino-3-(1-imino-2,2,2-trifluoroethyl)hexa-
fluoroindenes gave fluorinated 1,2,3,4-tetrahydro-1,3-
diazafluorene derivatives [2]. With the goal of extend-
ing the synthetic potential of compound I and its
analogs for the preparation of other polyfluoro-1,3-di-
azafluorene derivatives we examined reactions of I
with carboxylic acid anhydrides and chlorides.
fluorene (III), and 5,6,7,8,9,9-hexafluoro-2-[perfluoro-
(4-tolyl)]-4-trifluoromethyl-1,3-diazafluorene (IV),
respectively (Scheme 1). In addition, 1-(2-aminohexa-
fluoro-1H-inden-3-yl)-2,2,2-trifluoroethanone (V) was
isolated.
Presumably, the reaction involves initial acylation
of enaminoimine I at one nitrogen atom, and the
subsequent dehydration leads to compounds II–IV
(cf. [4]). Aminoketone V is likely to be formed via
hydrolysis of initial compound I by the action of water
and hydrogen chloride liberated during the condensa-
tion. In fact, compound I was converted into V in the
system H2O–CH2Cl2/HCl even at ~20°C. Apart from
products II and V, in the reaction of I with benzoyl
chloride we isolated N-(3-trifluoroacetylhexafluoro-
1H-inden-2-yl)benzamide (VI). By special experiment
we showed that compound VI is formed by ben-
zoylation of aminoketone V.
By heating compound I [3] with benzoyl, penta-
fluorobenzoyl and perfluoro(4-toluoyl) chlorides we
obtained 5,6,7,8,9,9-hexafluoro-2-phenyl-4-trifluoro-
methyl-1,3-diazafluorene (II), 5,6,7,8,9,9-hexafluoro-
2-pentafluorophenyl-4-trifluoromethyl-1,3-diaza-
Scheme 1.
F3C
F
F3C
F
F3C
F3C
NH
O
O
N
ArCOCl, 100–110°C
(RCO)2O, ~20°C
Ar(R)
+
+
N
F
NH2
F
F
F
NH2
F
F
NHCOPh
II–IV, VII, VII
H2O–CH2Cl2 (H+), ~20°C
V
VI
PhCOCl, 105°C
I
V
VI
II, Ar = Ph; III, Ar = C6F5; IV, Ar = 4-CF3C6F4; VII, R = Me; VIII, R = CF3.
1070-4280/04/4003-0421 © 2004 MAIK “Nauka/Interperiodica”

KARPOV et al.
422
45 Hz. This is the result of close spatial arrangement of
the F3 and F5 atoms. On the other hand, the coupling
constant between CF3 and F4 in amide VI is 6 Hz,
indicating that the interacting nuclei are fairly distant
from each other and that there is no intramolecular
hydrogen bonding between the amide proton and
carbonyl oxygen atom of the trifluoroacetyl group.
When such a hydrogen bond exists (as in compound
V), the corresponding coupling constant is 42 Hz [3].
Despite numerous crystallographic data for various
compounds containing a fluorene fragment (more than
500 structures deposited to the Cambridge Structural
Database [5]), we were the first to determine the mole-
cular and crystalline structure of 1,3-diazafluorene
derivatives (compounds II, III, VII, and VIII). The
1,3-diazafluorene fragment therein is planar within
±0.041(3), ±0.054(4), ±0.068(3), and ±0.065(5) Å,
respectively (Fig. 1), and the bond lengths mostly
coincide within the experimental error (Table 1). It
should be noted that replacement of the methyl group
in VII by trifluoromethyl (compound VIII) leads
to shortening of the C2–N3 bond from 1.336(5) to
1.310(6) Å and elongation of the C2–C14 bond from
1.506(6) to 1.532(8) Å. Quantum-chemical simulation
of such replacement by the PM3 semiempirical method
with pyrimidine as an example gives shortening of the
N1–C2 and C2–N3 bonds by 0.009 Å and elongation of
the C2–C14 bond by 0.057 Å.
Fig. 1. Structure of the molecule of 5,6,7,8,9,9-hexafluoro-2-
pentafluorophenyl-4-trifluoromethyl-1,3-diazafluorene (III)
according to the X-ray diffraction data.
Compound I reacted with acetic and trifluoroacetic
anhydrides at room temperature to give, respectively,
5,6,7,8,9,9-hexafluoro-2-methyl-4-trifluoromethyl-1,3-
diazafluorene (VII) and 5,6,7,8,9,9-hexafluoro-2,4-
bis(trifluoromethyl)-1,3-diazafluorene (VIII). Unlike
the reactions with acetic anhydride and aroyl chlorides,
only a small amount of V was formed in the reaction
with trifluoroacetic anhydride. A probable reason is
that the latter is the most electrophilic among the
acylating agent used, and the acylation and subsequent
cyclization of I are much faster than its hydrolysis.
The structure of compounds II, III, and VI–VIII
was established by X-ray analysis and was confirmed
Molecule II is almost planar: the angle between the
planes of the phenyl ring and 1,3-diazafluorenone
fragment is 2.4(1)°, while the angle between the
pentafluorophenyl ring plane and 1,3-diazafluorene
moiety in molecule III is 40.5(2)°. Molecules of II
in crystal give rise to infinite ladder chains via
arene–polyfluoroarene π-stacking interaction between
the phenyl ring of one molecule and tetrafluoro-
phenylene fragment of the other. The distance between
the centers of the interacting rings is 3.630 Å, the
average interplanar distance is 3.52 Å, and the dihedral
angle is 3.1°. The chains are arranged in layers, and the
interchain interaction is weaker than the interaction
between molecules in the chain: the distance between
the centers of the benzene ring and tetrafluoro-
phenylene fragment is 4.070 Å.
1
(including compound IV) by the 19F and H NMR
spectra (for compound VII, also by the 13C and 15N
NMR spectra). A specific feature of the 19F NMR
spectra of diazafluorenes II–IV, VII, and VIII is
a large coupling constant J(CF3,F5) which is equal to
Fig. 2. Structure of the molecule of 2-benzoylamino-
1,1,4,5,6,7-hexafluoro-3-trifluoroacetyl-1H-indene (VI)
according to the X-ray diffraction data. Selected bond
lengths (Å) and torsion angles (deg): C1–C8 1.490(3),
C1–C2 1.519(3), C2–C3 1.340(3), C2–N1 1.377(3), C3–C9
1.485(3), C3–C17 1.500(3), C8–C9 1.394(3), C10–N1 1.367(3),
C10–O1 1.212(2), C10–C11 1.480(3), C9C3C17C18 88.2,
C3C2N1C10 8.2, C2N1C10C11 179.0, N1C10C11C16 –5.0.
Slightly shortened [6] intramolecular F···F contacts
(2.721 Å) between the CF3 groups of compound VIII
in crystal give rise to formation of infinite zigzag
chains along the b axis. Except for C18 and O2, all
atoms in molecule VI lie almost in one plane
(the mean-square deviation is 0.051 Å; fluorine
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 3 2004

SYNTHESIS AND MOLECULAR AND CRYSTALLINE STRUCTURE
423
Table 1. Selected bond lengths (d) and bond and dihedral
angles (ω, φ) in molecules II, III, VII, and VIIIa
and hydrogen atoms were not taken into consideration;
Fig. 2). Molecules VI in crystal are linked in pairs to
form centrosymmetric dimers due to arene–polyfluoro-
arene π-stacking interaction; the distance between the
ring centroids is 3.622 Å, the average interplanar
distance is 3.54 Å, and the angle is 5.1°.
d, Å, or ω (φ),
II
III
VII
VIII
deg
N1–C10
N1–C2
C2–N3
C2–C14
N3–C4
C4–C11
C4–C20
C5–C6
1.312(4) 1.315(5) 1.315(4) 1.316(6)
1.342(4) 1.340(6) 1.336(5) 1.333(7)
1.345(4) 1.335(5) 1.336(5) 1.310(6)
1.483(4) 1.479(6) 1.506(6) 1.532(8)
1.340(4) 1.335(5) 1.333(4) 1.339(6)
1.384(4) 1.402(5) 1.386(5) 1.392(7)
1.526(4) 1.504(6) 1.500(5) 1.494(8)
1.376(5) 1.392(6) 1.370(5) 1.374(8)
1.378(4) 1.376(5) 1.375(4) 1.389(7)
1.376(5) 1.366(6) 1.374(5) 1.355(9)
1.377(5) 1.367(6) 1.386(5) 1.374(9)
1.360(4) 1.376(6) 1.353(5) 1.366(8)
1.491(4) 1.492(6) 1.497(5) 1.504(8)
1.504(4) 1.500(6) 1.499(5) 1.504(7)
1.400(4) 1.394(5) 1.404(4) 1.388(6)
1.494(4) 1.492(5) 1.478(5) 1.490(6)
1.402(4) 1.398(5) 1.406(4) 1.384(7)
114.9(3) 114.0(3) 114.4(3) 113.4(4)
124.6(3) 125.6(4) 125.1(4) 127.4(5)
118.5(3) 118.8(3) 118.8(3) 117.9(5)
121.5(3) 120.9(3) 121.6(3) 120.6(4)
EXPERIMENTAL
1
The 19F and H NMR spectra were recorded on
a Bruker WP-200SY spectrometer at 188.3 and
200 MHz, respectively, and the 13C and 15N NMR
spectra of compound VII were obtained on a Bruker
DRX-500 instrument at 125.8 and 50.7 MHz, respec-
tively. The chemical shifts are given downfield to
C6F6 (19F), TMS (1H, 13C), or liquid NH3 (15N); C6F6
and HMDS (δ 0.04 ppm) or CDCl3 (δC 76.9 ppm)
were used as internal references, and CH3NO2
(δN 382.0 ppm) was external reference. The elemental
compositions were determined from the high-resolu-
tion mass spectra which were obtained on a Finnigan
MAT-8200 spectrometer.
C5–C12
C6–C7
C7–C8
C8–C13
C9–C13
C9–C10
C10–C11
C11–C12
C12–C13
C10N1C2
N1C2N3
C4N3C2
N3C4C11
N3C2C14C19
N3C4C20F12
X-Ray analysis was performed on a Bruker P-4
diffractometer (MoKα radiation, graphite mono-
chromator, θ/2θ-scaning to 2θ < 50°). Single crystals
were obtained at 30–70°C in an evacuated (2 mm)
sealed ampule. The principal crystallographic data
are given in Table 2. The structures were solved by
the direct method using SHELXS-97 program (the
structure of VIII was solved using SIR-97 software)
and were refined by the least-squares procedure in
anisotropic–isotropic approximation using SHELXL-
97 program. The positions of hydrogen atoms were
determined by the difference synthesis of electron
density. The coordinates of non-hydrogen atoms are
available from the authors; selected bond lengths and
bond angles are given in Table 1. Figure 1 shows
the molecular structure of compound III as an example
for II, III, VII, and VIII, and the structure of VI is
shown in Fig. 2.
1.8b
9.0b
–5.8c
–7.2c
0.8
1.9
42.9
06.8
a
b
c
For atom numbering, see Fig. 1.
N3C2C14H.
N3C2C14F.
using CHCl3 as eluent to isolate 0.19 g (0.45 mmol,
50%) of compound II, mp 168–169°C (from CH2Cl2–
1
hexane). H NMR spectrum (CDCl3), δ, ppm:
8.58 (2H, 2'-H, 6'-H ), 7.55 (3H). 19F (CDCl3), δF, ppm:
94.4 (CF3), 45.8 (9-F), 32.9 (5-F), 23.4 (8-F), 17.0
5,6,7,8,9,9-Hexafluoro-2-phenyl-4-trifluoro-
methyl-1,3-diazafluorene (II). A mixture of 0.3 g
(0.9 mmol) of compound I and 0.38 g (2.7 mmol) of
benzoyl chloride was heated for 7 h at 100–110°C.
According to the 19F NMR data, a mixture of
compounds II, V, and VI was obtained at a ratio of
~62:11:27. The mixture was treated with a solution of
potassium hydroxide and extracted with methylene
chloride, the extract was washed with water, dried over
MgSO4, and evaporated, and the residue (0.32 g) was
subjected to column chromatography on silica gel
(6-F), 14.1 (7-F); JFF, Hz: J4-CF ,5 = 45, J5,6 = 19, J5,7
=
8, J5,8 = 15, J6,7 = 18, J6,8 = 7, J37,8 = 21, J8,9 = 5. Found:
M+ 420.03035. C18H5N2F9. Calculated: M 420.03089.
5,6,7,8,9,9-Hexafluoro-2-pentafluorophenyl-4-
trifluoromethyl-1,3-diazafluorene (III). A mixture of
0.2 g (0.6 mmol) of compound I and 0.41 g (1.8 mmol)
of pentafluorobenzoyl chloride was heated for 5 h at
100–105°C. According to the 19F NMR data, the
resulting mixture contained compounds III and V at
a ratio of ~1.5:1). The mixture was treated with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 3 2004

KARPOV et al.
Table 2. Crystallogaphic parameters of compounds II, III, and VI–VIII
424
Parameter
Formula
II
III
VI
C18H6F9NO2
439.24
VII
C13H3F9N2
358.17
VIII
C18H5F9N2
420.24
C18F14N2
510.20
Rhombic
Pca21
C13F12N2
412.15
Molecular weight
Crystal system
Monoclinic
C2/c
Rhombic
Pbca
Monoclinic
C2/c
Rhombic
P212121
Space group
Unit cell parameters:
a, Å
11.491(2)000
9.5306(19)
29.605(7)000
99.721(9)
3195.6(12)
8 (1.747)
12.5042(12)
14.257(2)22
10.1004(11)
9.5999(7)
15.8623(11)
22.0493(12)
39.914(15)
7.054(2)
9.529(3)
101.55(3)
2628.8(16)
8 (1.810)
0.199
9.0756(4)
9.7105(7)
b, Å
c, Å
15.8801(11)
β, deg
V, Å3
1800.6(4)
4 (1.882)
0.215
3357.6(4)
8 (1.738)
0.181
1399.49(15)
4 (1.956)
0.231
Z (dcalc, g/cm3)
µ, mm–1
0.178
Crystal habit, mm
0.45×0.45×0.12 0.09×0.40×0.90 1.2×0.60×0.60 0.15×0.56×1.0 0.15×0.45×0.90
Number of reflections,
total/independent
2902/2751
1678/1678
2933/2933
2349/2315
1436/1436
Number of reflections
1811
1319
2396
1317
1109
with I > 2σ(I)
Number of refined
0283
0308
0296
0218
0245
parameters
R for I > 2σ(I)
R1 = 0.0509
wR2 = 0.1332
R1 = 0.0834
wR2 = 0.1543
1.012
R1 = 0.0339
wR2 = 0.0761
R1 = 0.0495
wR2 = 0.0836
1.065
R1 = 0.0373
wR2 = 0.0960
R1 = 0.0476
wR2 = 0.1032
1.044
R1 = 0.0500
wR2 = 0.1345
R1 = 0.0885
wR2 = 0.1632
1.024
R1 = 0.0459
wR2 = 0.1317
R1 = 0.0603
wR2 = 0.1436
1.065
R for all reflections
GOOF
Not taken into
account
Correction for absorption
By facet
By facet
By facet
Semiempirical
a solution of potassium hydroxide and extracted with
methylene chloride, the extract was washed with
water, dried over MgSO4, and evaporated, and the
residue (0.16 g) was subjected to column chromatog-
raphy on silica gel using chloroform as eluent to
isolate 0.14 g (0.27 mmol, 46%) of compound III,
mp 85–86°C (from hexane). 19F NMR spectrum
(CHCl3), δF, ppm: 94.7 (CF3), 45.3 (9-F), 34.8
(5-F), 24.6 (8 F), 18.3 (6-F), 16.9 (7-F), 21.1 (2'-F,
(0.71 mmol) of perfluoro(4-toluoyl) chloride. Yield
0.13 g (0.23 mmol, 39%), mp 117.5–119°C (after
vacuum sublimation at 120°C/5 mm). 19F NMR spec-
trum (CHCl3), δF, ppm: 94.7 (CF3), 45.2 (9-F), 35.1
(5-F), 24.8 (8-F), 18.5 (6-F), 17.4 (7-F), 105.2
(4'-CF3), 22.9 and 22.7 (2'-F, 3'-F, 5'-F, 6'-F); JFF, Hz:
J4-CF ,5 = 45, J5,6 = 19, J5,7 = 9, J5,8 = 15, J6,7 = 18, J6,8
=
8, J73,8 = 21, J8,9 = 5. Found: M+ 559.98123. C19N2F16.
Calculated: M 559.98058.
6'-F ), 13.2 (4'-F), 1.4 (3'-F, 5'-F); JFF, Hz: J4-CF ,5 = 45,
1-(2-Aminohexafluoro-1H-inden-3-yl)-2,2,2-tri-
fluoroethanone (V) (by hydrolysis of compound I). To
a solution of 0.07 g (0.21 mmol) of compound I in
1 ml of methylene chloride we added 1 ml of water
and 2 drops of concentrated hydrochloric acid, and the
mixture was stirred for 20 h at ~20°C. The organic
phase was separated, washed with water, dried over
MgSO4, and transferred onto a watch glass to isolate
J
5,6 = 19, J5,7 = 9, J5,8 = 15, J6,7 = 18, J6,8 = 8, J73,8 = 21,
J8,9 = 5. Found: M+ 509.98337. C18N2F14. Calculated:
M 509.98378.
5,6,7,8,9,9-Hexafluoro-2-(heptafluoro-4-tolyl)-4-
trifluoromethyl-1,3-diazafluorene (IV) was syn-
thesized as described above for compound III from
0.2 g (0.6 mmol) of enaminoimine I and 0.2 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 3 2004

SYNTHESIS AND MOLECULAR AND CRYSTALLINE STRUCTURE
425
2JCF = 13, 3JCF = 3 Hz), 142.4 d.t (C7, 1JCF = 263, 2JCF
=
0.065 g (0.19 mmol, 92%) of compound V. The IR and
19F NMR spectra of the product coincided with those
of an authentic sample [3].
1
14 Hz), 120.5 s (C4a), 119.8 q (CF3, JCF = 275 Hz),
2
2
117.3 t.d (C8a, JCF = 24, JCF = 14 Hz), 117.2 t (C9,
1JCF = 250 Hz), 116.8 d (C4b, JCF = 14 Hz), 25.5 q
2
N-(1,1,5,6,7,8-Hexafluoro-3-trifluoroacetyl-1H-
inden-2-yl)benzamide (VI). A mixture of 0.06 g
(0.18 mmol) of compound V and 0.03 g (0.21 mmol)
of benzoyl chloride was heated for 7 h at 100–105°C.
The product was extracted into methylene chloride,
and the extract was washed with water, dried over
MgSO4, and transferred onto a watch glass. After
evaporation of the solvent, the residue (0.075 g) was
a mixture of compounds V and VI at a ratio of ~1:3
(CH3, 1JCH = 129 Hz). 15N NMR spectrum (CDCl3), δN,
ppm: 293.2 (N1), 290.8 q (N3, JNF = 4.7 Hz). Found:
3
M+ 358.01395. C13H3N2F9. Calculated: M 358.01524.
5,6,7,8,9,9-Hexafluoro-2,4-bis(trifluoromethyl)-
1,3-diazafluorene (VIII). A solution of 0.337 g
(1 mmol) of compound I in 1.27 g (6 mmol) of
trifluoroacetic anhydride (mixing of the reactants was
accompanied by spontaneous heating to ~40°C) was
kept for 18 h at ~20°C. The resulting solution con-
tained compounds V and VIII at a ratio of ~1:10
(according to the 19F NMR data). The solution was
transferred onto a watch glass, and the solid residue
(0.385 g) was subjected to chromatography on silica
gel using chloroform as eluent to isolate 0.296 g
(0.71 mmol, 71%) of compound VIII, mp 92–93°C
(vacuum sublimation at 95°C/20 mm), and 0.026 g
(0.08 mmol, 8%) of enaminoketone V, mp 158–159°C
(in a sealed capillary). The IR and 19F NMR spectra of
product V were identical to those reported in [3].
19
(according to the F NMR data). The product mixture
was subjected to column chromatography on silica
gel using chloroform as eluent to isolate 0.04 g
(0.09 mmol, 50%) of compound VI, mp 169–170°C
1
(from CH2Cl2–hexane). H NMR spectrum (acetone),
δ, ppm: 11.09 (NH), 8.01 quasi-d (2H, 2'-H, 6'-H,
J = 7.6 Hz), 7.69 quasi-t (1H, 4'-H, J = 7.6 Hz),
7.56 quasi-t (2H, 3'-H, 5'-H, J = 7.6 Hz). 19F NMR
spectrum (acetone), δF, ppm: 86.3 (CF3), 48.3 (1-F),
21.7 (7-F), 20.7 (4-F), 15.2 (5-F), 7.3 (6-F); JFF, Hz:
J
1,7 = 4.5, J3,4 = 6, J4,5 = 19, J4,6 = 3, J4,7 = 15, J5,6 = 17,
J5,7 = 7, J6,7 = 20.5. Found: M+ 439.02687.
C18H6NF9O2. Calculated: M 439.02547.
Compound VIII. 19F NMR spectrum (CHCl3), δF,
ppm: 95.0 (4-CF3), 91.9 (2-CF3), 45.3 (9-F), 36.0
(5-F), 25.2 (8-F), 18.9 (6-F), 18.3 (7-F); JFF, Hz:
5,6,7,8,9,9-Hexafluoro-2-methyl-4-trifluoro-
methyl-1,3-diazafluorene (VII). A solution of 0.5 g
(1.5 mmol) of compound I in 0.94 g (9.2 mmol) of
acetic anhydride was kept at ~20°C. According to the
19F NMR data, after 45 h, the mixture contained
compounds V and VII at a ratio of ~35:50 and ~15%
of initial enaminoimine I; after 135 h, compound I
disappeared. The mixture was transferred onto a watch
glass, and the solid residue (0.48 g) was subjected to
column chromatography on silica gel using chloroform
as eluent to isolate 0.26 g (0.73 mmol, 48%) of
diazafluorene VII, mp 112–113°C (from hexane), and
0.15 g (0.45 mmol, 30%) of ketone V.
J4-CF ,5 = 45, J5,6 = 19, J5,7 = 10, J5,8 = 15, J6,7 = 18,
3
J6,8 = 8, J7,8 = 21, J8,9 = 5. Found: M+ 411.98698.
C13N2F12. Calculated: M 411.98697.
The authors are grateful to the Russian Foundation
for Basic Research (project no 02-07-90322) for
providing the possibility of accessing the Cambridge
Structural Database.
REFERENCES
1. Haas, A., Hoppmann, E., Karpov, V.M., Platonov, V.E.,
and Shakirov, M.M., J. Fluorine Chem., 2000, vol. 102,
p. 313.
2. Karpov, V.M., Platonov, V.E., and Chuikov, I.P., Russ. J.
Org. Chem., 2003, vol. 39, p. 1151.
3. Chuikov, I.P., Karpov, V.M., and Platonov, V.E., Izv.
Akad. Nauk SSSR, Ser. Khim., 1990, p. 1856.
4. Petrova, O.E., Kurykin, M.A., and Gorlov, D.V., Izv.
Ross. Akad. Nauk, Ser. Khim., 1999, p. 2195.
5. Allen, F.H., Acta Crystallogr., Sect. B., 2002, vol. 58,
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1
Compound VII. H NMR spectrum (CDCl3), δ,
ppm: 2.95 (CH3). 19F NMR spectrum (CDCl3), δF,
ppm: 94.7 (CF3), 45.5 (9-F), 33.1 (5-F), 23.6 (8-F),
17.2 (6-F), 14.7 (7-F); JFF, Hz: J4-CF ,5 = 45, J5,6 = 19,
J5,7 = 8, J5,8 = 15, J6,7 = 18, J6,8 = 7, 3J7,8 = 21, J8,9 = 5.
13C NMR spectrum (CDCl3), δC, ppm: 169.9 q (C2,
2JCH = 7 Hz), 166.5 t (C9a, 2JCF = 24 Hz), 149.7 q (C4,
1
2
2JCF = 39 Hz), 145.2 d.d.t (C8, JCF = 260, JCF = 12,
3JCF = 93 Hz), 144.8 d.d.d.d (C6, 1JCF = 260, 2JCF = 17,
6. Zefirov, Yu.V. and Porai-Koshits, M.A., Zh. Strukt.
Khim., 1980, vol. 21, no. 4, p. 150.
2JCF = 13, JCF = 4 Hz), 144.1 d.d.d (C5, JCF = 263,
3
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 3 2004