Polyfluorinated arylnitrosamines

Article abstract of DOI:10.1016/S0022-1139(01)00567-X

N-Methyl-, N-n-butyl-, N-t-butylperfluoroarylamines undergo nitrosation with nitrous acid to give the corresponding N-nitroso derivatives. Perfluoroaryl groups were selected from the benzene, indane, biphenyl, naphthalene and pyridine series. According to

Full text of DOI:10.1016/S0022-1139(01)00567-X

Journal of Fluorine Chemistry 114 A2002) 55±61
Poly¯uorinated arylnitrosamines
Vyacheslav E. Platonova,*, Alois Haasb,1, Meinolf Schelvisb, Max Liebb,
Kira V. Dvornikovaa, Olga I. Osinaa, Tatyana V. Rybalovaa, Yuri V. Gatilova
aN.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, 9 Lavrentieva Avenue, 630090 Novosibirsk, Russia
b
È È È
Fakultat fur Chemie, Ruhr-Universitat Bochum, FNO 034/036, D-44780 Bochum, Germany
Received 17 September 2001; received in revised form 25 October 2001; accepted 31 October 2001
Dedicated to Prof. DWA. Sharp, on the occasion of his 70th birthday
Abstract
N-Methyl-, N-n-butyl-, N-t-butylper¯uoroarylamines undergo nitrosation with nitrous acid to give the corresponding N-nitroso derivatives.
1
Per¯uoroaryl groups were selected from the benzene, indane, biphenyl, naphthalene and pyridine series. According to H and 19F NMR
spectra, N-nitroso-N-methyl derivatives of poly¯uoroarenes consist of E and Z isomers with the former prevailing. The more bulky n-butyl
group promotes an increase in the formation of Z isomers. Only Z isomers have been obtained from N-t-butyl derivatives of per¯uorinated
4-toluidine and 4-aminopyridine. The structure of the Z isomer of N-nitroso-N-methylper¯uoro-4-toluidine is con®rmed by X-ray data.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Per¯uoroaromatic chemistry; Nitrosation; N-nitroso-N-methyl-; N-nitroso-N-n-butyl-; N-nitroso-N-t-butylper¯uoroarylamines; E and Z isomers;
X-ray crystal structure of N-nitroso-N-methylper¯uoro-4-toluidine
1. Introduction
2. Results and discussion
Recently, interest in nitrosamines has increased in con-
nection with the elucidation of their role as biologically
active compounds [1]. Usually, s-nitrosamines are obtained
by interaction of s-amines with nitrous acid. This method
was used for the synthesis of N-nitrosodialkyl-, N-nitro-
soalkylaryl- and N-nitrosodiarylamines [2,3].
As it turned out, nitrosation of N-alkylper¯uoroarylamines
was smoothly effected by HNO2 prepared in situ from sodium
nitrite in hydrochloric or acetic acid AScheme 1):
In the reaction of N-methylpenta¯uoroaniline A1) with
HNO2, N-nitroso-N-methylpenta¯uoroaniline A2) was obtai-
ned AScheme 2).
Earlier, N-nitroso-N-acetylpenta¯uoroanilide was descri-
bed. Its synthesis was achieved by interaction of penta¯uoro-
acetanilide with NOCl in the medium of the mixture of acetic
acid and acetic anhydride in the presence of CH3COOK and
P2O5 [4].
We have shown that N-alkylper¯uoroarylamines react
with nitric acid to give the corresponding N-nitroderivatives
and small amounts of N-nitroso-N-alkylper¯uoroarylamines
[5]. This induced us to carry out nitrosation of N-alkylper-
¯uoroarylamines by HNO2 in order to synthesize various
N-nitroso-N-alkylper¯uoroarylamines and investigate their
structures.
When the tri¯uoromethylhomologues of A1), such as
N-methyl-per¯uoro-4-toluidine A3) and N-methyl-per-
¯uoro-2,4-xylidine A4) were taken, nitrosation resulted in
N-nitroso-N-methyl-per¯uoro-4-toluidine A5) and N-nitroso-
N-methyl-per¯uoro-2,4-xylidine A6) AScheme 3). N-Methyl-
5-aminoper¯uoroindane A7) can be formally considered as
an analogue of N-methyl-per¯uoro-3,4-xylidine. In the reac-
tion of 7 with HNO2, N-nitroso-N-methyl-5-aminoper¯uor-
oindane A8) was obtained AScheme 4).
The transformation of N-methyl-4-cyanotetra¯uoroani-
line A9) and N-methyl-4-aminotetra¯uoropyridine A10)
by HNO2 into the corresponding N-nitroso derivatives A11
and 12) also demonstrates the synthetic range of N-nitrosa-
tion in the poly¯uoroaromatic series, as does the synthe-
sis of N-nitroso-N-methyl-4-aminonona¯uorobiphenyl A13)
and 4,40-bisAN-nitroso-N-methylamino)octa¯uorobiphenyl
A14) from N-methyl-4-aminonona¯uorobiphenyl A15) and
4,40-bisAN-dimethylamino)octa¯uorobiphenyl A16), and the
* Corresponding author. Tel.: ‡7-3832-34-4437; fax: ‡7-3832-34-4752.
E-mail addresses: platonov@nioch.nsc.ru AV.E. Platonov),
alois.haas@ruhr-uni-bochum.de AA. Haas).
1 Co-corresponding author. Tel.:‡49-234-32-23003x4;
fax: ‡49-234-32-14541.
0022-1139/02/$ ± see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 A 0 1 ) 0 0 5 6 7 - X

56
V.E. Platonov et al. / Journal of Fluorine Chemistry 114 72002) 55±61
Scheme 1.
Scheme 6.
Nitrosation of N-n-butylpenta¯uoroaniline A19) and N-n-
butylper¯uoro-4-toluidine A20) gave N-nitroso-N-n-butyl-
penta¯uoroaniline A21) and N-nitroso-N-n-butylper¯uoro-
4-toluidine A22)AScheme 6).
N-Nitroso-N-n-butyl-4-aminotetra¯uoropyridine A23) is
synthesized from N-n-butyl-4-aminotetra¯uoropyridine A24).
Scheme 2.
Scheme 3.
Interaction of N-t-butylper¯uoro-4-toluidine A25) and N-t-
butyl-4-aminotetra¯uoropyridine A26) with HNO2 resulted
in the formation of the corresponding N-nitroso derivatives
A27) and A28), which were stable as compared with the
corresponding N-nitro derivatives [5]. Conditions for nitro-
sation of N-alkylper¯uoroarylamines are given in Table 1.
Scheme 4.
Scheme 5.
conversion of N-methyl-2-amino-hepta¯uoronaphthalene
A17) to N-nitroso-N-methyl-2-aminohepta¯uoronaphthalene
A18) AScheme 5).
We have recently shown that nitration of bisAper¯uoro-4-
tolyl)amine affords the corresponding N-nitro derivative [5].
At the same time, an attempt at nitrosation of this amine by
HNO2 failed to show the corresponding N-nitroso derivative.
The presence of E and Z isomers of compound 2 was
1
found by comparison of H NMR spectra of these isomers
with the corresponding non-¯uorinated analogues described
in [6]. Proton chemical shifts of E and Z isomers of
compound 2 and its non-¯uorinated analogue are shown
in Scheme 7. According to this assignment, compound 2
consists of E and Z isomers A2E and 2Z) in the ratio of ꢀ2.3/1.
19F NMR data of the previously described N-nitroso-N-
acetylpenta¯uoroanilide [4] and 2Z isomer are in close
agreement with each other. This could suggest the formation
of the Z isomer of N-nitroso-N-acetylpenta¯uoroanilide. In
the 19F NMR spectrum of the 2Z isomer the chemical shift
of the ortho ¯uorine atoms is down®eld as compared to the

V.E. Platonov et al. / Journal of Fluorine Chemistry 114 72002) 55±61
57
Table 1
Preparation of N-nitroso-N-alkylperfluoroarylamines 2, 5, 6, 8, 11±14, 17, 21±23, 27 and 28
Compound
number
Amine Ag)
NaNO2 Ag)
Molar ratio HCl ACH3COOH, ml) Temperature A8C) Time Ah) Isolated product
Compound
number
Yield Ag) Yield A%)
1
1
2.0
25
2.0
17.5
0.2
1/1.45
1/2
A20)
200
A5)
20
10
10
3
18±24
0
20
1
2
2
1.85
25.5
80
77
58
94
90
64
3
0.5
2.0
1.0
1.0
0.3
0.2
0.3
0.25
0.5
0.5
0.5
0.57
0.5
1.2
0.5
1/1.45
1/2
1/2
18±22
20
2
5
0.32
2.1
3
1.1
À10 to 10
À7 to 0
À4 to 10
À5 to 5
22
5
4
0.46
0.45
0.23
0.4
1
6
1.0
7
1/2
1
8
0.7
a
9
1/2
1
±
0.25
0.17
0.23
0.2
9
1/2
1/2
2
3
11
12
13
14
18
21
22
23
27
28
74
65
73
75
63
59
56
85
93
75
10
15
16
17
19
20
24
25
26
0.23
0.1
3
0
1
1/2
3
À5 to 0
À2 to 0
À2 to 0
À4 to 0
20 to 22
À2 to 0
20 to 22
À2 to 0
1
0.31
0.24
0.29
0.18
0.31
0.36
0.31
1/2
5
1
0.43
0.35
0.33
0.35
0.43
1.05
0.43
1/2
1/2
5
2
5
1
1/1.5
1/2
A6)
5
20
3
1/1.5
1/2
A12)
5
20
1
a 11/9 ꢀ 2.4/1 according to NMR spectra.
2E isomerAapproximately by 5 ppm). A similar down®eld
shift of the ortho ¯uorine atoms relative to N-nitroso-N-
methyl group takes also place in other Z isomers: 5Z, 11Z,
12Z, 13Z ATable 2). A down®eld shift of the ortho ¯uorine
atoms was also used to assign the structures of the others Z
isomers. The ratio of E and Z isomers of N-nitroso-N-
alkylamino derivatives of per¯uoroarenes are given in Sec-
tion 3 and Table 2.
Scheme 7.
In the case of N-nitroso-N-methylaniline, the E isomer
with the phenyl group trans to the nitroso group is 104 times
Table 2
19F and 1H NMR data for N-nitroso-N-alkylperfluoroarylamines 2, 5, 11±14, 21±23, 27 and 28:
Compound
number
Ratio AE/Z)
E/Z chemical shifts Appm)
2,6-F Amultiplet)
3,5-F Amultiplet)
4-F
CH3
2
5
2.3/1
2.8/1
3/1
15.5/20.4
17.1/23.1
18.3/24.5
13.9/21.1
16.0/21.5
16.1/21.7
16.5/21.0
1.05/1.00
23.1/23.1
9.7 At, J ˆ 20.5 Hz)/10.8 At, J ˆ 20.5 Hz)
3.33/4.15
3.37/4.17
105.9/105.7 Amultiplet)
11
12
13a
14
21c
31.0/30.7
±
3.37/4.18
5.5/1
3/1
3b/1
74.3/74.3
±
3.41/4.21
3.43/4.21
23.0±25.3
25.5/25.2, 25.5/26.0
1.1/1.3
±
±
3.53/4.32, 3.53/4.31
0.82/0.91
0.56/1
10.0 Att, J ˆ 20.7 and 1.5 Hz)/11.3
Att, J ˆ 20.5 and 2.5 Hz)
22c
23c
27
0.74/1
1.1/1
Z
17.6/22.5
14.7/21.1
23.9
22.9/22.9
74.4/74.4
22.2
105.6/105.6Amultiplet)
0.89/0.98
0.84/0.93
1.64
±
105.4 At, J ˆ 21.7 Hz)
28
Z
21.5
74.1
±
1.64
a Chemical shift of signals p-C6F5: ꢀ23.0±25.3 Am, 2Fo), 12.6 Att, 1F, J ˆ 20:5 and 3.2 Hz, Fp), 1.8 Am, 2Fm).
b The ratio of E and Z isomeric contributions. Formally, it can mean that the ratio of E,E0/‰E; Z0ꢁE0; Z† ‡ Z; Z0Š ˆ 1/1.
c Other proton chemical shifts for the CH2a±CH2b±CH2g±CH3 group Aa, b, g, respectively)Ð21E: 3.82, 1.41, 1,23; Z: 4.49, 1.66, 1.41; 22E: 3.82, 1.45,
1.25; Z: 4.55, 1.72, 1.45; 23E: 3.92, 1.44, 1.23; Z: 4.58, 1.70, 1.44. For E isomers: Ha At, J ꢀ 7:2±7.3 Hz), Hb Am), Hg Am), H, CH3 At, J ꢀ 6:7±6.8 Hz); for Z
isomers: Ha At, J ꢀ 7:2±7.3 Hz), Hb Att, J ꢀ 7:2 Hz), Hg Am), H, CH3 At, J ꢀ 7:2±7.3 Hz).

58
V.E. Platonov et al. / Journal of Fluorine Chemistry 114 72002) 55±61
more abundant than the Z isomer [6]. An explanation of this
result consists in conjugation of the p systems of the phenyl
and nitroso groups lowering the total energy of the E isomer.
The phenyl group of the latter is considered to be coplanar
with the nitrosoamine group. In the Z isomer with the phenyl
group cis to the nitroso group, steric hindrance prevents
coplanarity, thus, making this isomer much less favorable
energetically [6]. Steric hindrance in 2Z with the penta-
¯uorophenyl group cis to the nitroso group can be more than
in the Z isomer of N-nitroso-N-methylaniline taking into
account the sizes of F and H [7]. Therefore, we would also
expect the formation of small amounts of 2Z as compared
with 2E. However, the difference between the ratio of E/Z for
2 A2.3/1) and N-nitroso-N-methylaniline A104/1) is large.
This difference cannot be explained by steric hindrance of
the penta¯uorophenyl group cis to the nitroso group in 2Z. A
steric interaction of the N-methyl substituent with the more
bulky penta¯uorophenyl group could prevent coplanarity
of penta¯uorophenyl ring with the nitrosoamine group to
some extent and reduce conjugation of the p systems of the
penta¯uorophenyl and nitroso groups, thus, making the 2E
isomer relatively less favorable energetically. This effect
may also be expected in the 2Z isomer. In addition, steric
hindrance in 2Z with the penta¯uorophenyl group cis to the
nitroso one could prevent coplanarity. The relatively small
difference in the ratio of 2E and 2Z as compared with the
difference in the ratio of E and Z isomers of N-nitroso-N-
methylaniline favors the former effect. The ratio of E and Z
isomers of N-nitroso-N-alkylper¯uoroarylamines changes
with increase in steric bulk of the N-alkyl substituent
AScheme 8). Thus, N-nitroso derivatives 21 and 22 contain-
ing n-butyl groups consist of E and Z isomer with the latter
prevailing. In the case of 23, the quantity of E and Z isomers
is close to each other. N-Alkylamino derivatives containing
the still more bulky t-butyl group give as N-nitroso deriva-
tive only the Z isomer Acompounds 27 and 28). Thus, the
following change of the relationship of isomers takes place
in the series of N-nitroso derivatives of N-methyl-, N-n-
butyl-, N-t-butylaminopoly¯uoroarenes AScheme 8).
Scheme 9.
Scheme 10.
data of work comparing NMR spectra of N-nitrosoamines
and carbenium ions [8] AScheme 9). More steric hindrance
in 2Z than in the Z isomer of N-nitroso-N-methylaniline
prevents coplanarity to a greater extent. Resonance contri-
bution AC) could be reduced by this effect and by the
resonance structure AD) AScheme 10). In this case, a decrease
of repulsion between the negative charges of the penta¯uor-
ophenyl ring and on the oxygen atom AA-like structure) can
be expected. In consequence, an increase of 2Z compared
with 2E isomer could occur. In 27Z the nitrosoamine group is
practically orthogonal to the benzene ring according to X-ray
data AFig. 1). In this case, the contribution of a resonance
structure C is practically impossible and unfavorable inter-
action of negative charges in structure like A can be small.
Therefore, the formation of Z isomer could be expected.
The larger contribution of the 12E isomer as compared
with 5E could be explained by the stronger unfavorable
interaction Arepulsion) of negative charges in the tetra¯uor-
opyridine ring and on the oxygen atom; it can re¯ect a more
strongly electron-withdrawing tetra¯uoropyridyl group than
per¯uorotolyl [9].
The form in which the more bulky alkyl group is trans to
the NO group was found for N-alkyl-N-methylnitrosoamines
[6].
Other effects may also be taken into account when the
difference in the ratio of E/Z for 2 and N-nitroso-N-methy-
laniline is examined. One may expect for the Z isomer of
N-nitroso-N-methylaniline that unfavorable interaction
Arepulsion) of negative charges in the phenyl ring and on
oxygen atom can arise as a result of conjugation AA). A con-
tributionofresonance structure AB)isproposedonthe basis of
It is possible that these factors can in¯uence the formation
of E and Z isomers in the course of the conversion of the
intermediate
E into poly¯uorinated arylnitrosamines
AScheme 10). Other factors, for example inductive effect
of ¯uorine atoms, intramolecular hydrogen bonds, the acid
medium could also have an in¯uence on the formation of E
and Z isomers of poly¯uorinated arylnitrosamines.
3. Experimental
19F and 1H NMR spectra were recorded on a Bruker AC-
200 instrument at 188.3 and 200 MHz in CHCl3 solution.
Scheme 8.

V.E. Platonov et al. / Journal of Fluorine Chemistry 114 72002) 55±61
59
Fig. 1. ORTEP diagram of N-nitroso-N-t-butylperfluoro-4-toluidine A27).
The standards were hexa¯uorobenzene A162.9 ppm from
CCl3F) and hexamethyldisiloxane A0.04 ppm from TMS).
IR spectra were measured on a UR-20 spectrophotometer for
solutions in CCl4. UV spectra were recorded on a Specord
UV±VIS instrument for solutions in ethanol. Molecular
weights of nitroso compounds were determined by mass
spectrometrically on a Finnigan MAT-8200 instrument. The
nominal energy of the ionizing electrons was 70 eV. X-ray
structure analysis was performed on a Bruker P4 diffract-
ometer Al, Mo Ka, graphite monochromator) at À30 8C.
The structure of N-nitroso-N-alkylper¯uoroarylamines was
established on the basis of 1H and 19F NMR, IR, UV spectral
data, molecular weights and elemental analyses. An assign-
22.1 Add, 1F, J ˆ 21:8 and 13.2 Hz, 6-F); dH ppm: 4.12.
Ratio of E/Z ꢀ 2:5/1. A8E) dF ppm: 55.2 and 54.7 Abroa-
dened peaks, 2F and 2F, 1-CF2, 3-CF2), 39.7 Am, 1F, 4-F),
34.1 Ad, broadened peaks, 1F, J ꢀ 20 Hz, 6-F), 32.1 Am, 2F,
2-CF2), 23.9 Att, 1F, J ˆ 20 and 7 Hz, 7-F); dH ppm: 3.39.
A8Z) dF ppm: 55.3 and 54.5 Abroadened peaks, 2F and 2F,
1-CF2, 3-CF2), 45.0 Am, 1F, 4-F), 39.8 Am, 1F, 6-F), 32.1 Am,
2F, 2-CF2), 23.3 Att, 1F, J ˆ 20 and 7 Hz, 7-F); dH ppm: 4.20.
Ratio of E/Z ꢀ 2:5/1. A18E) dF ppm: 36.1 Add, 1F, J ˆ 66
and ꢀ16 Hz, 1-F), 19.5 Abroadened peak, 1F, 3-F), 19.0 Adt,
1F, J ˆ 66 and ꢀ16 Hz, 8-F), 17.1 and 16.0 Adt, 1F and 1F,
J ˆ 58 and ꢀ16 Hz, 4,5-F), 10.8 and 8.3 Am, 1F and 1F, 6,7-
F). dH ppm: 3.42. A18Z) dF ppm: 41.7 Add, 1F, J ˆ 66 and
ꢀ16 Hz, 1-F), 23.4 Abroadened peak, 1F, 3-F), 19.0 Adt, 1F,
J ˆ 66 and ꢀ16 Hz, 8-F), 17.1 and 15.3 Adt, 1F, J ˆ 58 and
ꢀ16 Hz, 4,5-F), 10.8 and 7.8 Am, 1F and 1F, 6,7-F); dH ppm:
4.25. Ratio of E/Z ꢀ 2:5/1. NMR spectra of other N-nitro-
soamines are given in Table 2.
1
ment of signals in the H NMR spectra to E and Z isomers
was carried out by comparison with data described in
literature for non-¯uorinated N-nitrosoamines [6]. The ¯uor-
ine signals in the 19F NMR spectra were assigned by
comparison with 19F NMR data of the corresponding start-
ing compounds [5]. Comparisons of values of 2,6-F shifts in
isomeric N-nitroso-N-n-butyl- and N-nitroso-N-t-butylper-
¯uoroarylamines with 2,6-F of N-nitroso-N-methylper¯uor-
oarylamines make it possible to assign E or Z isomers for
compounds 21±23, 27 and 28. This assignment was con-
®rmed by X-ray structure analysis of 27Z AFig. 1).
IR and UV spectral and analytical data for N-nitroso-N-
alkylper¯uoroarylamines, and physical characteristics are
given in Table 3.
3.2. X-Ray analysis of N-nitroso-N-t-butylperfluoro-4-
toluidine 727)
3.1. N-Nitroso-N-alkylperfluoroarylamines
According to X-ray data AFig. 1) nitrosoamine group is
practically orthogonal to the benzene ring plane Adihedral
angle is 89.4A2)8, Fig. 1). The atoms O1 and N2 have
Awater solution of NaNO2 Aꢀ20%) was added to a stirred
mixture of N-alkylper¯uoroarylamine in acid AHCl or
CH3COOH). After reaction, cold water was poured into
the reaction mixture. The mixture was extracted with chloro-
form. The chloroform layer was washed with water, dried
over MgSO4, the solvent distilled off and the residue was
sublimed Adetails are given in Table 1). Compounds 6E, 6Z,
8E, 8Z, 17E, and 17Z showed the following NMR charac-
teristicsÐA6E) dF ppm: 105.7 Ad, 3F, J ˆ 23:8 Hz, 2-CF3),
105.4 At, 3F, J ˆ 22:8 Hz, 4-CF3), 49.9 Am, 1F, 3-F), 37.3 Am,
1F, 5-F), 20.1 Add, 1F, J ˆ 21 and 13 Hz, 6-F); dH ppm: 3.32.
A6Z) dF ppm: 103.2 Ad, 3F, J ˆ 23:2 Hz, 2-CF3), 105.3 At, 3F,
J ˆ 23:0 Hz, 4-CF3), 49.4 Am, 1F, 3-F), 37.3 Am, 1F, 5-F),
Ê
maximum deviations by 0.008A6) and À0.009A5) A, respec-
tively from the average plane of O1, N1, N2, C1, and C8
atoms. Bond lengths of the N±N=O fragment are close to the
corresponding ones of 3.3-dibenzyl-1AE)-nitroso-1-A2-toly-
l)urea [10], for example. No short intermolecular contacts
were found in the crystal.
Ê
Ê
Monoclinic system, a ˆ 6:102ꢁ2† A, b ˆ 21:340ꢁ5† A,
Ê
Ê 3
c ˆ 10:410ꢁ3† A, b ˆ 97:95ꢁ2†8, V ˆ 1342:4ꢁ6† A , space
group P21/n, C11H9F7N2O, M ˆ 318:20, Z ˆ 4, Dc ˆ
1:574 g cmÀ3, m ˆ 0:168 mmÀ1, FA0 0 0† ˆ 640, crystal
size 0:05 mm  0:10 mm  0:20 mm. Intensities of 1226
independent re¯ections were measured by y/2y-scans. No

Table 3
Elemental analyses, IR and UV data for N-nitroso-N-alkylperfluoroarylamines 2, 5, 6, 8, 11±14, 17, 21±23, 27 and 28
Compound C A%)
H A%)
F A%)
N A%)
Molecular weight
Calculated
Molecular
formula
Melting point
A8C)Abp A8C), mmHg) Arf, ±N±N =O
IR AcmÀ1),
UV, lmax Anm), Alog e)
number
Found Calculated Found Calculated Found Calculated Found Calculated Found
2
5
37.62 37.17
34.92 34.78
33.36 33.13
35.43 35.50
41.16 41.20
34.80 34.45
41.93 41.71
40.58 40.58
42.66 42.31
44.74 44.78
41.90 41.51
43.27 43.03
41.29 41.51
42.86 43.03
1.32
1.05
0.84
0.90
1.29
1.51
0.86
1.46
0.92
3.37
2.83
3.14
2.83
3.49
1.33
1.09
0.92
0.89
1.29
1.44
0.80
1.45
0.96
3.36
2.62
3.59
2.83
3.59
42.10 42.03
47.90 48.19
52.60 52.45
50.36 50.59
32.53 32.62
36.42 36.36
45.80 45.72
36.75 36.71
42.66 42.31
35.50 35.44
41.71 41.82
30.14 30.28
41.92 41.82
30.91 30.23
12.57 12.39
9.73 10.14
226.01655 226.01698 C7H3F5N2O A62.5/2)
276.01335 276.01342 C8H3F7N2O 42±43
326.01024 326.01016 C9H3F9N2O 40±40.5
308.01090a 308.01217 C10H3F9N2O 40±42
233.02153 233.02122 C8H3F4N3O 48.5±49
209.01991 209.02122 C6H3F4N3O A63/2)
344.01137a 344.01217 C13H3F9N2O 108±109
384.03680a 384.03830 C14H6F8N4O 143±144
282.01550a 282.01536 C11H3F7N2O 60±61
238.06370a 238.06551 C10H9F5N2O A70/2)
1480±1540
1430±1510
1460±1520
1480±1520
1480±1510
1450±1510
1475±1550
1460±1550
1430±1510
1470±1530
1470±1540
1450±1550
1480±1520
1450±1525
224 A3.77), 245 A3.77), 374 A2.33)
210 A3.81), 250 A3.91), 374 A2.28)
240 A3.55), 280 A3.40), 370 A2.52)
210 A4.13), 253 A3.97), 374 A2.30)
264 A3.86), 350 A2.00)
6
8.61
7.66
8.59
8.29
8
11
12
13
14
18
21
22
23
27
28
18.00 18.02
19.72 20.09
207 A3.85), 254 A3.97), 356 A2.20)
250 A3.89), 375 A1.70)
7.22
13.41 13.53
9.02 8.97
10.47 10.45
7.87 8.80
17.32 16.73
8.51 8.80
17.31 16.73
7.49
205 A4.27), 266 A4.42), 370 A2.60)
215 A4.58), 243 A4.03), 372 A2.38)
209 A4.02), 246 A3.90), 373 A2.20)
210 A3.88), 248 A3.85), 373 A2.23)
247 A3.60), 262 A3.62), 380 A1.70)
211 A3.88), 238 A3.78), 372 A2.30)
207 A3.72), 237 A3.75), 376 A2.08)
318.06016 318.06030
C11H9F7N2O A73/2)
251.06869 251.06817 C9H9F4N3O A70/2)
288.06226a 288.06231 C11H9F7N2O 21±28
221.06950a 221.07018 C9H9F4N3O 83±84
a These compounds did not give molecular ions in their MS spectra, so molecular weights were only determined for the fragment ions ArfNAlk AM±NO).

V.E. Platonov et al. / Journal of Fluorine Chemistry 114 72002) 55±61
61
Table 4
Atomic coordinates AÂ104) and equivalent isotropic displacement para-
®nal atomic parameters are collected in Table 4. The crystal
data have been deposited at the Cambridge Crystallographic
Data Centre Adeposition number CCDC 153993).
Ê 2
meters AA Â 103) for N-nitroso-N-t-butylperfluoro-4-toluidine A27)
Atom
x
y
z
U Aequivalents)
O1
N1
N2
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
F1
7767A11)
5695A10)
6933A14)
5496A14)
3889A15)
3744A17)
5230A2)
6861A16)
6982A16)
5200A3)
4581A15)
3490A3)
2770A3)
6130A2)
2396A8)
2131A10)
8379A10)
8646A8)
5332A15)
6670A18)
3330A2)
2943A4)
3227A3)
3395A4)
2590A4)
2209A4)
1585A4)
1301A4)
1671A6)
2297A5)
624A6)
6044A6)
4313A6)
5415A8)
3991A7)
4395A7)
4147A8)
3468A9)
3075A8)
3341A9)
3134A13)
3511A8)
2266A13)
4127A16)
3290A2)
5087A5)
4589A5)
2408A5)
2931A5)
1951A8)
3834A9)
3353A11)
114A2)
67A2)
Acknowledgements
100A3)
60A2)
The authors thank Volkswagenstiftung for ®nancial sup-
port of this work.
71A2)
79A3)
90A3)
88A3)
76A2)
References
140A5)
76A2)
3745A4)
3501A6)
3989A8)
4216A7)
2471A2)
1257A3)
1412A3)
2619A3)
495A3)
[1] R.G. Coombes, in: I.O. Sutherland AEd.), Comprehensive Organic
Chemistry, Vol. 2, Pergamon Press, Oxford, 1979, p. 365.
[2] S. Hauptmann, J. Graefe, H. Remane, Lehrbuch der Organischen
Chemie, VEB Deutscher Verlag fuÈr Grundstoffindustrie ARussian
transl.), Leipzig, 1979, p. 489.
198A7)
236A9)
294A14)
97A2)
F2
F3
126A2)
125A2)
107A2)
175A3)
212A4)
228A5)
[3] H. Feuer AEd.), The Chemistry of the Nitro and Nitroso Groups
APart 2; Russian transl.), Interscience Publishers, New York, 1970,
p. 187.
F4
F5
F6
[4] L.S. Kobrina, N.V. Popkova, Izv. Sib. Otd. Akad. Nauk SSSR, Ser.
Khim. 12 A1973) 99±104.
304A3)
F7
343A4)
[5] V.E. Platonov, A. Haas, M. Schelvis, M. Lieb, K.V. Dvornikova, O.I.
Osina, Yu.V. Gatilov, J. Fluorine Chem. 109 A2001) 131±139.
[6] H.W. Brown, D.P. Hollis, J. Mol. Spectrosc. 13 A1964) 305±312.
[7] J.H. Clark, D. Wails, T.W. Bastock, Aromatic Fluorination, CRC
Press, Boca Raton, 1996, p. 4.
absorption corrections were applied. The structurewas solved
by direct methods using SHELXS-97 and then re®ned by
least squares in full matrix anisotropic approximation to
wR2 ˆ 0:2179, S ˆ 1:056 AR ˆ 0:0750 for 733Fo > 4sꢁF†)
using SHELXL-97. Large atomic thermal parameters of
t-butyl group and low crystal quality could be noted. The
[8] J.G. Traynham, M.T. Yang, Tetrahedron Lett. 10 A1965) 575±577.
[9] R.D. Chambers, P.A. Martin, J.S. Waterhouse, D.L.H. Williams, J.
Fluorine Chem. 20 A1982) 507±514.
[10] K. Yamaguchi, G. Matsumura, M. Tanno, S. Suayoshi, N. Miyata,
Acta Crystallogr. Sect. C ACr. Str. Commun.) 48 A1992) 1051±1054.