Reaction of perfluoro-2-methylpent-2-ene and perfluoro-5-azanon-4-ene with aniline and its derivatives

Article abstract of DOI:10.1016/S0022-1139(00)00247-5

Reaction of perfluoro-2-methylpent-2-ene (1) and perfluoro-5-azanon-4-ene (2) with aniline, 4-fluoroaniline, 4-methoxyaniline and 2,6-dimethylaniline in the presence of Et₃N provides derivatives of quinoline and quinozaline, whereas reaction of

Full text of DOI:10.1016/S0022-1139(00)00247-5

Journal of Fluorine Chemistry 104 (2000) 263±271
Reaction of per¯uoro-2-methylpent-2-ene and
per¯uoro-5-azanon-4-ene with aniline and its derivatives
Ki-Whan Chia, Georgii G. Furinb,*, Irina Yu. Bagryanskayb, Yurii V. Gatilovb
aDepartment of Chemistry, University of Ulsan, Ulsan 680-749, South Korea
bInstitute of Organic Chemistry, Russian Academy of Sciences, 630090 Novosibirsk, Russia
Received 14 December 1999; accepted 10 February 2000
Abstract
Reaction of per¯uoro-2-methylpent-2-ene (1) and per¯uoro-5-azanon-4-ene (2) with aniline, 4-¯uoroaniline, 4-methoxyaniline and 2,6-
dimethylaniline in the presence of Et3N provides derivatives of quinoline and quinozaline, whereas reaction of 2 yields diazetine derivatives
with 2- and 4-nitroanilines, 2,6-dichloroaniline and penta¯uoroaniline. The structure of [2-(1,1,2,2,3,3,3-penta¯uoroethyl)-3-tri¯uor-
omethyl-quinoline-4-yl]-phenylamine is con®rmed by X-ray structural data. The routes of reactions and the 19F and 13C NMR spectral data
of the products are discussed. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: Per¯uoro-2-methylpent-2-ene; Per¯uoro-5-azanon-4-ene; Nucleophilic addition; Intramolecular nucleophilic cyclization; 2-derivatives of azetine;
Diazetine; Quinoline; Quinozaline; [2-(1,1,2,2,2-Penta¯uoroethyl)-3-tri¯uoromethylqinouline-4-yl]-phenylamine
1. Introduction
respectively, gave N-butyl-aminoper¯uoro-2,3,4-trimethyl-
4-ethyl-2-azetine or 3-(1-methylamino-1-tri¯uoromethyl-
per¯uoropropyl)-4-methyl-imino-N-methyl-2-tri¯uoro-
methyl-2-azetine [13]. Moreover, per¯uoro-2-methylpent-
2-ene (1) is known to react with tert-butylamine, iso-pro-
pylamine and n-propylamine to yield azetine derivatives
[12,14±16].
Fluorine-containing aromatic compounds have drawn
much attention because of their biological activities [1±
3]. Many of them are used as new medicines or pesticides as
themselves or as precursors for the synthesis of biologically
active compounds. For example, azoles and pyrimidines
with per¯uoroalkyl substituents have shown interesting
biological activities. This fact substantially triggers the
development of effective methods for the synthesis of
various heterocyclic systems with a ¯uorinated moiety,
especially a per¯uoroalkyl group. Among the known meth-
ods for the production of ®ve- and six-membered hetero-
cycles, heterocyclization by the reaction of binucleophilic
reagents with available internal per¯uoroole®ns has been
focused on as a useful methodology [4±7].
The azetine derivatives are also the prospective inter-
mediates for new antibiotics [8,9]. Synthesis of four-mem-
bered heterocycles has been performed by the reaction of
some internal per¯uoroole®ns with ammonia or primary
amines [10±16]. Thus, reaction of tetra¯uoroethylene trimer
with cyclohexylamine led to 1-cyclohexyl-2-tri¯uoro-
methyl-3-(2,2,2-tri¯uoroethylidene)-cyclohexylamino-4-N-
cyclohexyl-imino-2-azetine [10]. Treatment of per¯uoro-
3,4-dimethylhex-3-ene with butylamine or methylamine,
On the other hand, reaction of internal per¯uoroole®ns
with aniline has been noted to provide quinoline derivatives
[10,17,18]. Thus, treatment of aniline with 2H-hepta¯uor-
obut-2-ene produced phenyl-(2-tri¯uoromethyl-quinoline-
4-yl)amine [13] and reaction of aniline with tetra¯uoroethy-
lene trimer provided 2-tri¯uoromethyl-3-(1-N-phenylimino-
2,2,2-tri¯uoro-ethyl)-4-(N-phenylamino)quinoline [10]. The
presence of electron-donating substituents in aromatic
amines is supposed to facilitate the formation of quinoline
derivatives. Reaction of 1 with 2,4-dimethoxyaniline gave 4-
(2,4-dimethoxyanilino)-6,8-dimethoxy-2-penta¯uoroethyl-
3-tri¯uoromethylquinoline [17]. However, that kind of reac-
tion remains unclear yet since reaction of aniline with
octa¯uoro-3,4-bis(tri¯uoromethyl)hexa-2,4-diene yielded
1-phenyltetrakis(tri¯uoromethyl)-1H-pyrrole instead of
2,3,4,5-tetrakis(tri¯uoromethyl)-1H-benzo[b]-azetine [19].
To continue our research on the new methodology for the
synthesis of heterocycles starting with internal per¯uoro-
ole®ns, we have investigated in detail the reactions of 1 and
per¯uoro-5-azanon-4-ene (2) with aniline and its derivatives
* Corresponding author.
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 0 ) 0 0 2 4 7 - 5

264
K.-W. Chi et al. / Journal of Fluorine Chemistry 104 (2000) 263±271
Scheme 1.
4-¯uoroaniline, 2,6-dimethylaniline, 2,6-dichloroaniline, 4-
methoxyaniline, 2- and 4-nitroaniline and penta¯uoroani-
line. All reactions were carried out in the presence of
triethylamine.
shows centro-symmetrical pairs of molecules, bonded by p-
stacking interaction of the quinoline frameworks with inter-
Ê
plane distance 3.586(5) and 3.546(5) A.
The NMR spectral data of products 3±8 show the same
characteristic chemical shifts and coupling constants as
those described earlier for similar compounds. The proton
signals of compounds 3±8 are placed at 6.9±7.4 ppm, which
is a typical range for aromatic protons. The 19F NMR
spectrum reveals three groups of signals with a 3:3:2
intensity ratio; the chemical shifts for compound 3 are equal
2. Results and discussion
The compounds 1 and 2 have been found to react
smoothly with 2 equivalents of aniline, 4-¯uoroaniline
and 4-methoxyaniline in the presence of 3 equivalents of
Et3N in MeCN to give the compounds 3±8 (Scheme 1).
The structure of [2-(1,1,2,2,2-penta¯uoroethyl)-3-tri-
¯uoromethylqinoline-4-yl]-phenyl amine (3) was con®rmed
by X-ray analysis, infrared (IR), 1H, 13C, 19F NMR and mass
spectroscopy. The X-ray structure of quinoline 3 is pre-
sented in Fig. 1, which shows two rotamers in a single
crystal.
The tri¯uoromethyl group on C3 is disordered with the
relative occupation of positions equal to 0.868(6):0.132(6).
In the case of the second independent molecule, the disorder
does not take place. The geometry of both molecules
coincides with the limits of 3s, excluding the CF3
group. The quinoline framework has been found to be planar
Ê
in the limits of Æ0.055(3) and Æ0.063(3) A, respectively, for
both molecules. The bond lengths in 3 are rather close to
corresponding values in 4-anilino-2-diethoxyphosphonyl-3-
chloroquinoline [20], the closest structural analogue from
the Cambridge bank of structural data [21]. The different
orientation of the aniline fragment is signi®cant: the torsion
angles C10±C4±N14±C15 and C4±N14±C15±C16 in mole-
cule 3 are equal to 58.5(4), 58.6(4), 25.3(5) and 20.9(5)8,
whereas in 4-anilino-2-diethoxyphosphonyl-3-chloroquino-
line, they are equal to 132.2 and 15.28. The crystal packing
Fig. 1. The crystal structure of 3 as per X-ray analysis.

K.-W. Chi et al. / Journal of Fluorine Chemistry 104 (2000) 263±271
265
Scheme 2.
to 108.6 ppm (triplet JFFˆ10 Hz), 82.3 ppm (singlet) and
49.6 ppm (quartet JFFˆ10 Hz).
( 326.707 kcal/mol) of the six-membered ring 3 is sub-
stantially less than that of the four-membered ring 14
( 276.06 kcal/mol). The greater stability of 3 compared
to 14 should favor formation of the six-membered hetero-
cycle 3 under thermodynamically controlled conditions. On
the other hand, the calculation indicates that the negative
charge on the nitrogen atom in B (qNˆ 0.61e) is greater
than that on the carbon atom (qCˆ 0.23e) in the ortho-
position. This should facilitate the formation of intermediate
12 instead of 13.
In the actual system, the intramolecular nucleophilic
cyclization of B occurs via route b to form the six-mem-
bered ring 3. This indicates that the route of cyclic formation
of B is determined only by thermodynamic factors. A
similar reaction mechanism can be proposed for the reaction
of compound 2 with aniline. In this case, the major step
consists of the formation of the second C=N group to yield a
six-membered ring. Therefore, formation of the six-mem-
bered rings 3±8 from the reaction of 1 and 2 with the
substituted anilines might be rationalized if the route of
intramolecular cyclization is determined thermodynami-
cally.
Reaction of 1 with aniline begins presumably with the
attack of the N-nucleophile on the carbon atom of the double
bond to form anion A. The following transformations of A
might occur via two different routes (Scheme 2). Elimina-
tion of ¯uoride ion from A yields phenyl-[3,3,3-tri¯uoro-1-
(penta¯uoroethyl)-2-tri¯uoromethyl-propenyl]-amine (9 or
11). Enamine 9 undergoes enamine±imine isomerization by
Et3N to give the more stable imino isomer 10 [22]. The
elimination of ¯uoride ion from the CF3 fragment, however,
leads to the formation of phenyl-[1,3,3-tri¯uoro-1-(penta-
¯uoroethyl)-2-tri¯uoromethyl-allyl]-amine (11). Reaction
of 11 with Et3N provides anion B, and an intramolecular
cyclization is followed between the terminal double bond
and the N- or C-nucleophilic center of B (Scheme 3).
Intramolecular cyclization could occur by two different
ways to form 2,2-di¯uoro-4-(penta¯uoroethyl)-1-phenyl-
3-tri¯uoromethyl-1,2-dihydroazete (12) (route a) or 4-¯uoro-
2-(penta¯uoroethyl)-3-tri¯uoromethyl-quinoline (13)
(route b), respectively. Further reaction of 12 or 13 with
another aniline produces [4-(penta¯uoroethyl)-1-phenyl-3-
tri¯uoromethyl-1H-azet-2-ylidene]-phenylamine 14 or 3. It
would be reasonable to think that the selectivity between
routes a and b should be related to the nucleophilicity of the
attacking atom and the stability of the product. MNDO
(PM3, AM1) calculations show that the heat of formation
On the other hand, reaction of 2 with 2-nitro-, 4-nitro- or
penta¯uoroaniline produces the diazetine derivative (2-nitro-
phenyl)-[1-(2-nitrophenyl)-2,4-bis(hepta¯uoropropyl)-1,2-
dihydro-[1,3]-diazet-2-yl]-amine (16), (4-nitrophenyl)-[1-
(4-nitrophenyl)-2,4-bis(hepta¯uoropropyl)-1,2-dihydro-
Scheme 3.

266
K.-W. Chi et al. / Journal of Fluorine Chemistry 104 (2000) 263±271
Scheme 4.
[1,3]-diazet-2-yl]-amine (17) or (penta¯uorophenyl)-[1-
(penta¯uorophenyl)-2,4-bis(hepta¯uoropropyl)-1,2-dihy-
dro-[1,3]-diazet-2-yl]-amine (18), respectively (Scheme 4).
Formation of the four-membered rings 16±18 means that the
¯uorine atom in position 4 is substituted by the N-nucleo-
phile instead of the C-nucleophile. Obviously, an introduc-
tion of an NO2-group or ®ve F atoms to the aniline ring
lowers the nucleophilicity of the C-anionic center more than
that of the N-anionic one. This fact in combination with the
higher reactivity of ¯uoro-imine group derived from 2
makes the reaction proceed kinetically to give the diazetine
intermediate 15. Further substitution of the active ¯uorine
atom in 15 by aniline gives 16±18 (Scheme 4).
It is also interesting to note that reaction of 2 with 2,6-
dichloroaniline provides the diazete derivative 1-(2,6-
dichlorophenyl)-2-¯uoro-2,4-bis-(hepta¯uoropropyl)-1,2-
dihydro-[1,3]-diazete (19). However, treatment of 2 with
2,6-dimethylaniline produces a six-membered heterocycle
Ð the dihydroquinazoline derivative [2,4-bis-(hepta¯uoro-
propyl)-4a,8-dimethyl-2,4a-dihydroquinazolin-2-yl]-
(2,6-dimethylphenyl)-amine (20) (Scheme 5). Similarly,
Scheme 5.
reaction between 1 and 2,6-dimethylaniline yields the
dihydroquinoline 4,4-di¯uoro-4a,8-dimethyl-2-(penta-
¯uoroethyl)-3-tri¯uoromethyl-4,4a-dihydroquinoline (21)
(Scheme 6).
Reaction of 1 with penta¯uoroaniline produces a mixture
of products 22±25. The major product is 25, formed by the
addition of (penta¯uorophenyl)-[3,3,3-tri¯uoro-1-(penta-
¯uoroethyl)-2-tri¯uoromethylpropylidene]-amine (22) to a
double bond, probably because of the low reactivity of the
N-nucleophile. Also, the formation of compounds [3,3-
di¯uoro-1-(penta¯uoroethyl)-2-tri¯uoromethyl-allylidene]-
(penta¯uorophenyl)-amine (23) and (penta¯uorophenyl)-
[2,2,3,3,3-penta¯uoro-1-(20,20,20-tri¯uoroethyl)-propyli-
dene]-amine (24) is observed by GC-MS data (Scheme 6).
Scheme 6.

K.-W. Chi et al. / Journal of Fluorine Chemistry 104 (2000) 263±271
267
Table 1
4
3
a
Ê 2
Atomic coordinates (Â10 ) and equivalent isotropic displacement parameters (A Â10 ) for compound 3
Atom
x/a
Y/b
z/c
U (eq)b
Atom
x/a
y/b
z/c
9580(2)
U (eq)
N(1)
C(2)
3756(2)
2680(3)
2444(3)
3460(3)
5779(3)
6872(3)
6916(3)
5878(3)
4734(3)
4665(3)
1733(3)
2264(4)
1124(3)
3388(3)
3612(3)
3436(3)
3618(4)
3982(4)
4160(4)
3988(3)
673(2)
2131(2)
5071(2)
5145(2)
5659(2)
6025(2)
6245(2)
6155(2)
5743(3)
5403(2)
5485(2)
5936(2)
4589(2)
3927(3)
5909(3)
6423(2)
7350(2)
8068(2)
8964(2)
9161(3)
8448(3)
7543(3)
5167(2)
4033(2)
3288(2)
4383(2)
3435(2)
5678(4)
5569(3)
6857(2)
6260(2)
6362(19)
5035(14)
62(1)
59(1)
59(1)
56(1)
65(1)
75(1)
80(1)
72(1)
56(1)
55(1)
73(1)
92(1)
81(1)
71(1)
59(1)
66(1)
81(1)
90(1)
92(1)
78(1)
107(1)
102(1)
121(1)
133(1)
129(1)
145(2)
124(2)
124(2)
121(8)
111(8)
98(7)
N(1A)
C(2A)
C(3A)
C(4A)
C(5A)
C(6A)
C(7A)
C(8A)
C(9A)
C(10A)
C(11A)
C(12A)
C(13A)
N(14A)
C(15A)
C(16A)
C(17A)
C(18A)
C(19A)
C(20A)
F(1A)
2769(2)
2821(3)
1894(3)
804(3)
74(2)
7(2)
55(1)
54(1)
56(1)
55(1)
61(1)
69(1)
72(1)
65(1)
53(1)
51(1)
66(1)
76(1)
77(1)
68(1)
60(1)
76(1)
92(1)
94(1)
84(1)
68(1)
92(1)
83(1)
93(1)
110(1)
90(1)
102(1)
118(1)
130(1)
2583(3)
3614(3)
4239(2)
4338(3)
3819(3)
2721(3)
2172(3)
2691(3)
3773(2)
1891(3)
972(4)
8664(2)
8170(2)
8719(2)
10367(2)
11320(2)
11697(2)
11114(2)
10123(2)
9732(2)
8188(2)
8866(3)
7103(2)
8332(2)
8450(2)
8311(2)
8390(3)
8633(3)
8787(3)
8692(2)
7717(2)
7549(1)
9439(2)
8330(2)
9367(2)
6663(1)
6784(2)
6771(2)
C(3)
653(2)
C(4)
1297(2)
1914(2)
1949(3)
1410(3)
820(3)
C(5)
C(6)
390(3)
396(3)
C(7)
670(3)
C(8)
C(9)
1708(3)
1751(3)
706(2)
764(2)
C(10)
C(11)
C(12)
C(13)
N(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
F(1)
1345(2)
857(3)
3968(3)
4590(3)
2068(4)
230(3)
1721(3)
671(3)
4009(4)
5330(2)
5637(2)
4816(3)
5139(3)
6293(3)
7107(3)
6795(3)
1331(2)
2610(2)
1425(3)
107(2)
1844(2)
3053(2)
3436(4)
4612(4)
5391(4)
5005(3)
3837(3)
321(2)
715(3)
1967(3)
2448(4)
1692(5)
471(4)
33(3)
4963(2)
3608(2)
5189(2)
5486(2)
3718(2)
3287(2)
1688(3)
1391(3)
F(2)
1289(2)
3283(2)
2555(3)
1351(3)
168(2)
F(2A)
1539(2)
1217(2)
2492(2)
2304(2)
417(2)
F(3)
F(4)
F(3A)
F(4A)
F(5)
526(2)
F(5A)
F(6)
3320(4)
5061(3)
4125(4)
4910(2)
3320(2)
4024(18)
F(6A)
F(7)
F(8)
1090(3)
791(3)
F(7A)
F(8A)
1727(2)
54(3)
F(6Z)
F(7Z)
F(8Z)
1040(2)
320(2)
730(2)
aSecure positions for the atoms F(6), F(7), F(8) make up 0.868(6), and the atoms F(6Z), F(7Z), F(8Z), 0.132(6).
bU (eq) is defined as one-third of the trace of the orthogonalized Uij tensor.
In short, reaction of 1 or 2 with aniline or its derivatives
containing an electron-donating substituent proceeds to
form a six-membered heterocycle, whereas the presence
of a strongly electron-withdrawing substituent in aniline
facilitates the formation of four-membered heterocycles.
We consider that these experiments illustrate the potential of
using internal per¯uoroole®ns for the synthesis of hetero-
cyclic compounds containing per¯uoroalkyl groups
(Table 1).
recorded on a Bruker Vector spectrometer (5% in CCl4).
UV spectra were taken with a Carl/Zeiss Jena Specord M-
40. GC-MS spectra were obtained with the electron impact
mode at 70 eV and reported as m/z (relative intensity) using
a Finnigan MAT model 8200 spectrometer. Mass spectra
(Table 2) were obtained with a gas chromatograph electron
ionization detector (Hewlett±Packard G 1800A GCD sys-
tem), 30 m capillary column 0.25 mm in diameter with a
0.25 mk ®lm for co-polymer 5% diphenyl±95% dimethyl-
silicon (HP-5), gas: helium, 1 ml/min, column temperature:
2808C. All reactions were monitored routinely by 19F NMR
spectroscopy. Column chromatography was performed
using silica gel 60 (0.063±0.2 mm). Merck TLC plates with
silica gel 60 were used for TLC analysis with the indicated
solvents. Melting points were recorded at atmospheric
pressure and are uncorrected. All the commercially avail-
able reagents were of analytical grade and used without
further puri®cation. Compound 10 was also prepared by the
known procedure [22].
3. Experimental
3.1. Instrumentation
19F NMR spectra were recorded in ppm down®eld from
internal standard C6F6 in CDCl3 using a Bruker WP 200SY
spectrometer operating at 188.324 MHz. 13C NMR spectra
were recorded in ppm down®eld from internal standard
(Me4Si, d 0.00) using a Bruker AM 400 spectrometer
operating at 100.614 MHz in CDCl3 (JCH not recorded).
Coupling constants are given in Hz. IR spectra were
X-ray structure analysis was carried out on a Syntex P21
diffractometer using Cu Ka radiation with a graphite mono-
chromator. X-ray structure data for 3: C18H10F8N2, Mˆ

268
K.-W. Chi et al. / Journal of Fluorine Chemistry 104 (2000) 263±271
Table 2
Mass-spectral data for new compounds
Compound
m/e (Irel (%))
‡
‡
‡
‡
‡
‡
3
406 [M] (100), 387 [M±F] (11.92), 337 [M±CF3] (32.11), 317 [M±CF3±HF] (8.64), 268 [M±2CF3] (4.83), 145 [C2F5CN] (0.44),
‡
‡
‡
‡
‡
119 [C2F5] (2.40), 100 [CF2=CF2] (0.49), 77 [C6H5] (13.76), 76 [C6H4] (1.21), 69 [CF3] (1.69)
‡ ‡ ‡ ‡ ‡ ‡
4
5
442 [M] (100), 423 [M±F] (13.38), 422 [M±HF] (27.21), 403 [M±HF±F] (32.91), 373 [M±CF3] (10.80), 333 [M±FC6H4N] (17.93),
‡
‡
‡
‡
239 [FC6H3N=CC2F5] (0/83), 203 [FC6H4NHC=CCF3] (2.11), 169 [C3F7] (3.84), 119 [C2F5] (5.20), 110 [FC6H4NH] , 95 [FC6H4]
‡
(10.87), 69 [CF3] (18.58)
‡
‡
‡
466 [M] (2.37), 335 (55.49), 324 [M±OCH3C6H4NH±HF] (3.40), 310 (2.70), 216 (100), 122 [CH3OC6H4NH] (5.42), 107
‡
‡
‡
[CH3OC6H4] (19.29), 77 [C6H4] (25.31), 69 [CF3] (3.27)
‡ ‡ ‡ ‡ ‡ ‡
6
7
559 [M] (42.65), 540 [M±F] (4.82), 390 [M±C3F7] (100), 169 [C3F7] (0.71), 119 [C2F5] (1.00), 69 [CF3] (18.58)
595 [M] (40.42), 576 [M±F] (6.37), 426 [M±C3F7] (100), 365 [M±FC6H3N=CNHC6H4F] (7.25), 307 [C3F7C(NH2)NHC6H4F]
‡
‡
‡
‡
‡
‡
‡
‡
‡
‡
(7.84), 290 [C3F7C=NC6H4F] (26.59), 169 [C3F7] (5.92), 135 [FC6H3N=C=NH] (14.35), 119 [C2F5] (3.06), 95 [C6H4F] (45.82), 69
‡
[CF3] (10.82)
‡ ‡ ‡ ‡ ‡
8
619 [M] (10.01), 600 [M±F] (0.98), 450 [M±C3F7] (16.23), 328 [M±C3F7±CH3OC6H4NH] (0.72), 122 [CH3OC6H4NH] (63.54), 169
‡
‡
‡
‡.
‡
[C3F7] (9.50), 119 [C2F5] (6.95), 107 [CH3OC6H4] (5.69), 100 [CF2=CF2] (4.90), 69 [CF3] (17.17)
‡ ‡ ‡ ‡ ‡
18
19
22
649 [M] (5.36), 630 [M±F] (0.78), 480 [M±C3F7] (4.24), 446 [M±C3F7] (19.71), 334 (69.42), 288 (100), 169 [C3F7] (49.42), 148
‡
‡
‡
‡
‡
[C6H4(CN)NO2] (6.62), 138 [C6H4(NH2)NO2] (40.25), 119 [C2F5] (20.07), 100 [CF2=CF2] (7.48), 69 [CF3] (64.88)
‡
‡
‡
‡
‡
649 [M] (42.93), 630 [M±F] (6.28), 480 [M±C3F7] (100), 434 [M±C3F7±NO2] (12.60), 388 [M±C3F7±2NO2] (3.24), 317 (23.97), 169
‡
‡
‡
‡
[C3F7] (1.27), 119 [C2F5] (0.41), 76 [C6H4] (16.29), 69 [CF3] (2.75)
‡
‡
‡
‡
‡
615 [M] (36.95), 596 [M±F] (5.21), 496 [M±C2F5] (3.80), 446 [M±C3F7] (74.77), 343 (100), 316 (16.08), 300 (18.59), 169 [C3F7]
‡
‡
‡
(16.07), 148 (23.10), 130 (39.00), 122 [C3H3(CH3)2] (1.49), 121 (17.52), 119 [C2F5] (9.64), 100 [CF2=CF2] (3.74), 86 (39.13), 77
‡
(16.53), 69 [CF3] (29.03), 44 (66.60)
‡ ‡ ‡ ‡ ‡
24
25
463 [M] (26.70), 444 [M±F] (6.52), 344 [M±C2F5] (100), 324 [M±C2F5±HF] (13.68), 312 [M±(CF3)2CH] (19.38), 275 [M±C2F5±
‡
‡
‡
‡
‡
‡
CF3] (6.83), 212 [M±(CF3)2CH±CF2=CF2] (32.35), 193 [C6F5NC] (6.42), 167 [C6F5] (12.80), 131 [CF3C=CF2] (0.83), 119 [C2F5]
‡
‡
(11.85), 100 [CF2=CF2] (1.04), 69 [CF3] (18.25)
‡
‡
‡
‡
‡
‡
329 [M] (61.00), 310 [M±F] (3.27), 210 [M±C2F5] (53.01), 209 [C6F5NCO] (2.90), 182 [C6F5NH] (100), 167 [C6F5] (1.95), 162
‡
‡
‡
‡
‡
[M±C6F5] (8/09), 155 [C5F5] (42.55), 119 [C2F5] (42.01), 100 [CF2=CF2] (3.69), 69 [CF3] (40.58)
Ê
406.28, triclinic, space group P-1, aˆ10.569(2) A, bˆ
3.2.2. Synthesis of phenyl-[3,3,3-trifluoro-1-(1,1,2,2,2-
pentafluoroethyl)-2-trifluoromethylpropylidene] amine (9),
[2-(1,1,2,2,2-pentafluoroethyl)-3-trifluoromethylqinoline-4-
yl]-phenyl amine (3) and [2,4-bis(1,1,2,2,3,3,3-heptafluoro-
propyl)-1,2-dihydroquinozaline-2-yl]phenyl amine (6)
Ê
Ê
11.582(2) A, cˆ14.267(4) A, aˆ89.20(3)8, bˆ79.21(1)8,
gˆ81.82(1)8, Vˆ1698.0(5) A , Zˆ4, Dcalˆ1.592 g/cm3,
Ê 3
mˆ1.406 mm 1. 6475 intensities of independent re¯ections
were measured (y/2y-scan, 2y<1408) for a crystal sample
sealed in a polyethylene capillary. Evaporation (10% drop)
and empirical absorption (transmission 0.68±0.95) correc-
tions were applied. The structure was solved by direct
methods and re®ned in an anisotropic approximation using
program SHELXL-97. Riding model was used for hydrogen
atom re®nements. The ®nal R-factors are wR2ˆ0.1485,
Sˆ1.022 (Rˆ0.0530 for 4024 F>4s). Atomic coordinates,
thermal parameters, bond distances and angles have been
deposited at the Cambridge Crystallographic Data Centre.
Nonhydrogen atom coordinates are shown in Table 1.
1. The general procedure with 1 (15.0 g, 0.050 mol), Et3N
(15.2 g, 0.15 mol) and aniline (4.65 g, 0.05 mol) in
CH3CN (30 ml) provided 3 (13.2 g, 65% yield) and 10
(3.73 g, 20% yield).
[2-(1,1,2,2,2-Pentafluoroethyl)-3-trifluoromethylqi-
nouline-4-yl]-phenyl amine (3): bp 164±1658C (4 Torr);
1
mp 88±898C (from aq. alcohol). H NMR (CDCl3) dH
7.62 (d, H8, 8), 7.46 (d, H8, 8), 7.32 (t, H7, 8), 6.98 (t,
H6, 8), 6.54 (d, H15, 7.4), 6.56 (t, H17, 7.4), 6.78 (t, 16,
7.4). 13C NMR (CDCl3) dC 149.6 (C9), 146.4 (C10),
2
143.8 (C , JCFˆ28.1), 143.8 (C4), 131.4 (C8), 129.6
(C5), 128.4 (C7), 127.6 (C6), 124.7 (C14), 122.6 (C15),
122.8 (C11, 1JCFˆ274.0), 122.1 (C17), 118.5 (C16), 118.7
(C13, 1JCFˆ286.3; 2JCFˆ36.2), 112.1 (C12, 1JCFˆ259.6;
2
3.2. Reaction of the compounds 1 and 2 with aniline and
its derivatives in the presence of Et3N
3.2.1. General procedure
3
2JCFˆ34.6), 111.1 (C , JCFˆ33.1). 19F NMR (CDCl3)
dF 108.2 (F11, t, 23), 83.7 (F13, s), 55.3 (F12, q, 23). IR
3430 (N±H), 2900 (C±H); 1600 (C=N); 1565 (C=N);
1490 (C=CAr); 1415 (C=Car), 1370 and 1340 (N±C);
1310, 1110±1240 (C±F) [23]. HRMS calc. 406.0716 for
C18H10F8N2, found 406.0724. UV spectra, lmax
(C2H5OH) 350 nm (eˆ8400). Found (%): C, 53.22;
52.99; H, 2.33; 2.59; F, 37.58; 37.56; N, 6.74. Calc. (%):
C, 53.20; H, 2.46; F, 37.44; N, 6.90.
2
To a solution of 1 (or 2) and Et3N in MeCN (15±20 ml) at
08C was added dropwise a solution of aniline or its deri-
vative in MeCN (10 ml). The resulting solution was stirred
for 1±2 h at room temperature and then for 2±4 h at 458C.
The reaction mixture was washed with water (2 mlÂ50 ml),
neutralized with 5% aqueous H2SO4 and extracted with
CH2Cl2 (3 mlÂ50 ml). The concentrate was distilled under
reduced pressure to give a liquid, which was further puri®ed
by column chromatography (hexane/CH2Cl2).

K.-W. Chi et al. / Journal of Fluorine Chemistry 104 (2000) 263±271
269
Phenyl-[3,3,3-trifluoro-1-(1,1,2,2,2-pentafluor-
oethyl)-2-trifluoromethylpropylidene] amine (10): bp
368C (3 Torr); 1H NMR (CDCl3), dH 4.63 (m, H2), 6.58
3.2.4. Synthesis of [4-methoxy-2-(pentafluoroethyl)-3-
trifluoromethylquinolin-4-yl]-(4-methoxyphenyl)-amine (5)
The general procedure with 1 (6 g, 0.02 mol), Et3N
(6.06 g, 0.06 mol) and 4-methoxyaniline (4.9 g, 0.04 mol)
in MeCN (25 ml) gave 5: (6 g, 65% yield); bp 165±1688C
(Torr). 1H NMR (CDCl3) dH 6.92 (d, H8, 8), 6.86 (d, H5, 8),
6.77 (d, H7, 8), 7.34 (m, H15), 7.20 (m, H16), 5.26 (N±H),
3.66 (H18,19). 13C NMR (CDCl3) dC 158.1 (C9), 155.5 (C10),
148.8 (C4), 142.1 (C17), 141.1 (C2, 2JCFˆ29.4), 136.6 (C6),
130.9 (C14), 123.5 (C5), 123.0 (C7), 121.7 (C15), 120.4 (C11,
(m, H8, 7 Hz), 7.11 (H10, 7 Hz), and 7.26 (H9, 7 Hz). 13
C
NMR (CDCl3) dH: 151.7 (C3, JCFˆ32), 145.5 (C7),
2
125.6 (C10), 129.4 (C8), 120.3 (C1,6
,
1JCFˆ268.3;
2JCFˆ32.2), 117.9 (C9), 118.2 (C5, JCFˆ287.5;
1
4
2JCFˆ34.0), 110.0 (C , JCFˆ267.0; JCFˆ37.4), 50.4
1
2
(C , JCFˆ33.1). 19F NMR (CDCl3) dF 101.7 (6F, F1,6),
83.3 and 82.4 (3F, F5), 49.2 and 47.8 (2F, F4). IR 3090
and 3020 (C±H); 1670 (C=C); 1595 (C=CAr); 1490
(C=CAr); 1360 (N±C); 1340, 1290, 1100±1250 (C±F)
[23]. HRMS calc. 373.0325 for C12H6F11N, found
373.0239.
2
2
13
1
2
1JCFˆ264.4), 118.7 (C , JCFˆ286.2; JCFˆ36.4), 113.4
(C16), 112.3 (C12, JCFˆ258.7; JCFˆ34.4), 109.1 (C3,
2JCFˆ32.0), 103.1 (C8), 54.1 (C18,19). 19F NMR (CDCl3)
dF 105.4 (F11, t, 20), 81.0 (F13, s), 52.9 (F12, q, 20). IR 3446
(N±H), 3018, 2968 (C±H); 1621 (C=C); 1574 (C=N); 1509
(C=CAr); 1455 (C±N), 1428 (N±C) 1240±1188 (C±F) [23].
UV spectrum lmax 246 nm (eˆ41 500), 358 nm (eˆ6200).
HRMS calc. 466.0927 for C20H14F8N2O2, found 466.0928.
1
2
2. The general procedure with 2 (14 g, 0.032 mol), Et3N
(14 g, 0.14 mol) and aniline (6.2 g, 0.066 mol) in MeCN
(50 ml) gave 6 (12.1 g, 67% yield).
[2,4-Bis(1,1,2,2,3,3,3-heptafluoropropyl)-1,2-dihy-
droquinozaline-2-yl]phenyl amine (6); mp 89±908C
(hexane). 13C NMR (CDCl3) dC 145.8 (C4,
3.2.5. Synthesis of [6-fluoro-2,4-bis(heptafluoropropyl)-
1,2-dihydroquinazolin-2-yl]-(4-fluorophenyl)-amine (7)
The general procedure with 2 (8.6 g, 0.02 mol), Et3N
(6.06 g, 0.06 mol) and 4-¯uoroaniline (4.4 g, 0.04 mol) in
MeCN (15 ml) produced 7 (9.1 g, 77% yield); mp 126±
5
2
2
2JCFˆ10.8), 145.2 (C ), 140.5 (C , JCFˆ16.5), 133.5
(C6), 133.5 (C16), 132.8 (C17), 129.2 (C10), 128.4 (C6),
128.2 (C8), 125.5 (C18), 125.4 (C20), 122.5 (C19), 115.3
(C13,16
,
1JCFˆ287.8; JCFˆ33.7), 107.5 (C11,14
,
2
1
1JCFˆ263.4; JCFˆ40.4), 106.2 (C12,15
,
1JCFˆ268.3;
1278C (hexane). H NMR (CDCl3) dH 7.47 (N±H), 6.98
2
2JCFˆ35.5). 19F NMR (CDCl3) dF 82.8 (6F, F13,16), 43.7
(4F, F11,14), 36.9 (4F, F12,15). IR 3416 (N±H), 3029
(C±H); 1696 (C=N); 1650 (N=C); 1563 (C=CAr);
1512 (C=Car), 1450 and 1350 (N±C), 1230±1210
(C±F) [23]. HRMS calc. 559.0729 for C20H11F14N3,
found 559.0732. Found (%): C, 42.97; H, 2.27; F,
47.77; N, 7.52. Calc. (%): C, 42.93; H, 1.97; F, 47.58;
N, 7.51.
(Ph). 13C NMR (CDCl3) dC 159.6 (C7,20
,
1JCFˆ244.9),
158.6 (C4, JCFˆ22.3), 154.9 (C2, JCFˆ26.2), 131.7
2
2
(C17), 128.6 (C10), 126.6 (C18), 123.0 (C5), 122.6 (C19),
122.3 (C9), 117.0 (C13,16, JCFˆ286.8; JCFˆ33.7), 114.7
1
2
(C6,8, JCFˆ29.2), 110.4 (C11,14, JCFˆ263.4; JCFˆ40.4),
3
1
2
107.8 (C12,15, JCFˆ268.4; 2JCFˆ35.4). 19F NMR (CDCl3)
1
dF 81.9 (3F, F13), 81.8 (3F, F16), 42.8 and 41.9 (2F, F11), 44.1
and 42.8 (2F, F14, AB-system JFFˆ234 Hz), 35.8 (2F, F12),
35.4 (2F, F15). IR 3415 (N±H), 3140 (C±H); 1739 (C=N);
1696 (C=N); 1651 (C=CAr); 1540 and 1511 (C=Car), 1410
and 1350 (N±C), 1234±1200 (C±F) [23]. UV spectrum lmax
334 nm (eˆ1350). HRMS calc. 595.0541 for C20H9F16N3,
found 595.0540. Found (%): C, 40.46; H, 1.51; F, 50.47; N,
6.06. Calc. (%): C, 40.34; H, 1.51; F, 51.09; N, 7.06.
3.2.3. Synthesis of [4-fluoro-2-(1,1,2,2,2-pentafluoro-
ethyl)-3-trifluoromethylquinolin-4-yl]-(4-fluorophenyl)-
amine (4)
The general procedure with 1 (6 g, 0.02 mol), Et3N
(6.06 g, 0.06 mol) and 4-¯uoroaniline (4.4 g, 0.04 mol) in
MeCN (15 ml) provided 4 (7.3 g, 82.5% yield); mp 92±
938C (hexane). 1H NMR (CDCl3) dH 7.95 (d, H8, 8), 7.48 (d,
H5, 8), 6.90 (t, H7, 8), 6.90 (m, H15), 6.90 (m, H16), 5.26 (N±
3.2.6. Synthesis of [2,4-bis(heptafluoropropyl)-6-methoxy-
1,2-dihydroquinazolin-2-yl]-(4-methoxyphenyl)-amine (8)
The general procedure with 2 (8.6 g, 0.02 mol), Et3N
(6.06 g, 0.06 mol) and 4-methoxyaniline (4.9 g, 0.04 mol)
in MeCN (15 ml) gave 8 (8.9 g, 72% yield); mp 100±1018C
(CH2Cl2). 1H NMR (CDCl3) dH 7.47 (N±H), 6.98±7.11 (Ph),
3.72 (CH3O). 13C NMR (CDCl3) dC 158.4 (C4, 2JCFˆ28.6),
157.6 (C10), 156.8 (C5), 154.6 (C2, 2JCFˆ25.8), 144.6 (C7,20),
129.3 (C17), 128.4 (C8), 127.7 (C6), 124.2 (C19), 121.9 (C18),
13
6
1
H). C NMR (CDCl3) dC 159.6 (C , JCFˆ243.9), 151.4
(C17, JCFˆ252.7), 149.9 (C9), 139.6 (C10), 144.5 (C4),
1
143.9 (C2, JCFˆ29.9), 133.6 (C14, JCFˆ9.4), 123.8
2
3
(C15, JCFˆ10.1), 123.7 (C11, JCFˆ274.6), 122.4 (C16,
3
1
2JCFˆ25.9), 119.5 (C13, JCFˆ286.5; JCFˆ36.0), 116.5
1
2
(C7, JCFˆ23.0), 112.9 (C12, JCFˆ260.2; JCFˆ34.4),
2
1
2
112.3 (C , JCFˆ31.8), 109.6 (C , JCFˆ24.9). 19F NMR
(CDCl) dF 108.7 (F11, t, 20), 84.4 (F13, s), 55.7 (F12, q, 23).
IR 3438 (N±H), 3122 (C±H); 1629 (C=C); 1582 (C=N);
1500 (C=CAr); 1448 (C±N), 1408 and 1382 (N±C); 1339,
1313, 1230±1192 (C±F) [23]. UV spectrum lmax (C2H5OH)
348 nm (eˆ7460). HRMS calc. 442.0528 for C18H10F8N2,
found 442.0523. Found (%): C, 49.49; H, 1.99; F, 44.44; N,
6.24. calc. (%): C, 48.87; H, 1.81; F, 42.99; N, 6.33.
3
5
2
2
117.0 (C13,16, JCFˆ287.4; JCFˆ33.5), 113.7 (C9), 109.2
1
2
(C11,14
,
1JCFˆ261.3; JCFˆ30.2), 107.7 (C12,15
,
1JCF
ˆ
2
266.7; JCFˆ38.4), 54.1 (C21,22). 19F NMR (CDCl3) dF
82.08 (3F, F13), 82.5 (3F, F16), 43.6 (2F, F11), 43.1 (2F, F14),
36.7 (2F, F12), 36.4 (2F, F15). IR 3380 (N±H), 2902, 2941 (C±
H); 1693 (C=N); 1465 (C=CAr); 1230±1196 (C±F) [23].
HRMS calc. 619.0941 for C22H15F14N3O2, found 619.0938.
2

270
K.-W. Chi et al. / Journal of Fluorine Chemistry 104 (2000) 263±271
3.2.7. Synthesis of (2-nitrophenyl)-[1-(2-nitrophenyl)-2,4-
bis(heptafluoropropyl)-1,2-dihydro-[1,3]-diazet-2-yl]-
amine (16)
32.59; 32.68; H, 0.34; 0.39; F, 62.50; 62.32; N, 5.36; M
(mass spectrometry), 739. C20HF24N3: Calc. (%): C, 32.48;
H, 0.14; F, 61.71; N, 5.68; M, 739.
The general procedure with 2 (9.4 g, 0.02 mol), Et3N
(6.06 g, 0.06 mol) and 2-nitroaniline (3 g, 0.02 mol) in
MeCN (35 ml) provided 16 (9.02 g, 64% yield); mp 73±
748C (hexane). 1H NMR (CDCl3) dH 6.20 (N±H), 6.57±7.92
(Ph). 13C NMR (CDCl3) dC 155.5 (C2, 1JCFˆ274.0), 139.8
(C21), 144.8 (C15), 135.9 (C13), 135.3 (C19), 133.7 (C16),
131.3 (C14), 116.2 (C12), 118.6 (C11), 125.9 (C20), 125.6
3.2.10. Synthesis of 1-(2,6-dichlorophenyl)-2-fluoro-2,4-
bis-(heptafluoropropyl)-1,2-dihydro-[1,3]-diazete (19)
The general procedure with 2 (4.33 g, 0.01 mol), Et3N
(3.03 g, 0.03 mol) and 2,6-dichloroaniline (1.62 g,
0.01 mol) in MeCN (15 ml) provided 19 (2.4 g, 47% yield);
bp 112±1138C (0.5 Torr). 1H NMR (CDCl3) dH 1.08 (H18),
1.12 (H17), 1.52 (H10), 2.09 (H9), 2.79 (H8), 6.93±7.02 (Ph).
(C22), 121.9 (C18), 121.7 (C17), 115.3 (C7,10, JCFˆ287.8;
1
6
2JCFˆ33.6), 107.5 (C5,8
,
1JCFˆ263.4; JCFˆ40.2), 106.2
13C NMR (CDCl3) dC 161.9 (C , JCFˆ10.4), 159.4 (C2,
2JCFˆ15.9), 144.0 (C6), 130.4 (C8), 129.7 (C9), 129.0 (C10),
125.8 (C5), 129.1 (C22), 127.3 (C21), 116.4 (C19), 117.8
2
2
(C6,9, JCFˆ268.3; JCFˆ35.1). 19F NMR (CDCl3) dF 82.9
(F7), 82.7 (F10), 45.9 (F5), 44.9 (F8), 36.9 (F6), 36.7 (F9). IR
3400 (N±H), 3200 (C±H); 1703 (C=N); 1625 (N=C); 1435
and 1347 (NO2), 1288 (N±C), 1223±1123 (C±F) [23]. UV
spectrum (C2H5OH) lmax 231 nm (eˆ20 000), 273 nm
(eˆ6900), 404 nm (eˆ4300). HRMS calc. 649.0431 for
C20H9F14N5O4, found 649.0476.
1
2
(C20), 109.7 (C11,14, 1JCFˆ268.4; 2JCFˆ35.4), 118.0 (C13,16
,
1JCFˆ288.5; JCFˆ33.2), 108.5 (C12,15
,
1JCFˆ263.9;
2
2JCFˆ40.2), 16.7 (C23), 45.4 (C17,18). 19F (CDCl3) dF
82.4 (F16), 81.8 (F13), 48.8 (F14), 44.8 (F11), 38.0 (F15),
35.7 (F12). 3435 (N±H), 2986 (C±H); 1745 (C=C); 1697
(C=C); 1662 (C=N); 1506 and 1470 (C=Car), 1399 and 1349
(N±C); 1310, 1230±1125 (C±F) [23]. UV spectrum lmax
240 nm (eˆ8600). HRMS calc. 615.1355 for C24H19F14N3,
found 615.1340.
3.2.8. Synthesis of (4-nitrophenyl)-[1-(4-nitrophenyl)-2,4-
bis(heptafluoropropyl)-1,2-dihydro-[1,3]-diazet-2-yl]-
amine (17)
The general procedure with 2 (9.4 g, 0.02 mol), Et3N
(6.06 g, 0.06 mol) and 4-nitroaniline (3 g, 0.02 mol) in
MeCN (35 ml) produced 17 (9.6 g, 68% yield); mp 157±
3.2.11. Synthesis of [2,4-bis-(heptafluoropropyl)-4a,8-
dimethyl-2,4a-dihydroquinazolin-2-yl]-(2,6-dimethyl-
phenyl)-amine (20)
1
1588C (CH2Cl2). H NMR (CDCl3) dH 7.10 (N±H), 6.98±
4
8.19 (Ph). 13C NMR (CDCl3) dC 156.7 (C , JCFˆ10.2),
The general procedure with 2 (12.5 g, 0.029 mol), Et3N
(8.08 g, 0.08 mol) and 2,6-dimethylaniline (3.5 g,
0.029 mol) in MeCN (55 ml) produced 20 (10.8 g, 60.8%
yield); bp 150±1558C (0.4 Torr). 1H NMR (CDCl3) dH 1.08
(H18), 1.12 (H17), 1.52 (H10), 2.09 (H9), 2.79 (H8), 6.93±
2
153.9 (C2, JCFˆ16.2), 142.8 (C13), 140.4 (C12), 121.1
2
(C14), 122.7 (C11), 115.3 (C7,10, JCFˆ287.8; JCFˆ33.7),
1
2
107.5 (C5,8
,
1JCFˆ263.4; JCFˆ40.4), 106.2 (C6,9
,
2
1JCFˆ268.3, JCFˆ35.5). 19F NMR (CDCl3) dF 82.1 (F7),
81.7 (F10), 46.8 (F5), 46.0 (F8), 37.7 (F6), 35.9 (F9). IR 3373
(N±H), 3078 (C±H); 1696 (C=N); 1634 (N=C); 1585
(C=CAr); 1520 (C=Car), 1414 and 1344 (NO2), 1273±
1190 (C±F) [23]. UV spectrum lmax 205 nm (eˆ30 700),
317 nm (eˆ17 500), 401 nm (eˆ4700). HRMS calc.
649.0431 for C20H9F14N5O4, found 649.0418. Found (%):
C, 36.73; 36.70; H, 1.68; 1.95; F, 39.69; 39.80; N, 10.51.
Calc. (%): C, 36.98; H, 1.39; F, 40.99; N, 10.79.
2
6
7.02 (Ph). 13C NMR (CDCl3) dC 161.9 (C , JCFˆ10.4),
2
2
159.4 (C , JCFˆ15.9), 144.0 (C6), 130.4 (C8), 129.7 (C9),
2
129.0 (C10), 125.8 (C5), 129.1 (C22), 127.3 (C21), 116.4
(C19), 117.8 (C20), 109.7 (C11,14, JCFˆ268.4; JCFˆ35.4),
1
2
118.0 (C13,16
,
1JCFˆ288.5; JCFˆ33.2), 108.5 (C12,15
,
2
1JCFˆ263.9; JCFˆ40.2), 45.4 (C17,18), 16.7 (C23). 19F
NMR (CDCl3) dF 82.4 (3F, F16), 81.8 (3F, F13), 48.8 (2F,
F14), 44.8 (2F, F11), 38.0 (2F, F15), 35.7 (2F, F12). IR 3435
(N±H), 2986 (C±H), 1745 (C=C), 1697 (C=C), 1662 (C=N),
1506 and 1470 (C=Car), 1399 and 1349 (N±C), 1310, 1230±
1125 (C±F) [23]. UV spectrum lmax (C2H5OH) 240 nm
(eˆ8600). HRMS calc. 615.1355 for C24H19F14N3, found
615.1340.
2
3.2.9. Synthesis of (pentafluorophenyl)-[1-(pentafluoro-
phenyl)-2,4-bis(heptafluoropropyl)-1,2-dihydro-[1,3]-
diazet-2-yl]-amine (18)
The general procedure with 2 (5.6 g, 0.013 mol), Et3N
(5.3 g, 0.052 mol) and penta¯uoroaniline (4.8 g, 0.026 mol)
in MeCN (15 ml) gave 18 (5.5 g, 57% yield); bp 110±1158C
3.2.12. Synthesis of 4,4-difluoro-4a,8-dimethyl-2-
(pentafluoroethyl)-3-trifluoromethyl-4,4a-dihydroquinoline
(21)
The general procedure with 1 (8.7 g, 0.029 mol), Et3N
(8.08 g, 0.08 mol) and 2,6-dimethylaniline (3.5 g,
0.029 mol) in MeCN (40 ml) gave 21 (3.0 g, 27% yield);
bp 93±958C (0.4 Torr), mp 178±1798C (aq. C2H5OH).
1H NMR (CDCl3) dH 1.22 (H14, 7.3), 2.05 (H8, 7.3), 2.30
(H9, 7.3), 2.97 (H10, 7.3). 13C NMR (CDCl3) dC 153.2 (C6),
130.4 (C8), 129.7 (C9), 129.0 (C10), 125.8 (C5), 124.8 (C11,
(0.2 Torr). mp 117±1188C (CH2Cl2). 13C NMR (CDCl3) dC
158.4 (C2, JCFˆ25.9), 155.8 (C4), 140.5 (C9,14
,
2
1JCFˆ250.4), 137.2 (C10,14
,
1JCFˆ249.4), 135.7 (C15,
1JCFˆ240.4), 131.5 (C11, JCFˆ240.1), 130.3 (C8,
1
0
2JCFˆ33.7), 116.6 (C7;7 , JCFˆ287.5; JCFˆ33.6), 109.2
1
2
0
0
(C5;5 , JCFˆ264.4, JCFˆ32.5), 108.4 (C6;6 , JCFˆ275.4,
1
2
1
0
2JCFˆ30.9). 19F (CDCl3) dF 82.8 (F7), 82.1 (F7 ), 47.9 (F5),
0
44.2 (F5), 36.7 (F6), 36.4 (F6 ), 13.8 (F9), 12.3 (F13), 12.1
(F11), 12.1 (F15), 2.9 (F10), 3.6 (F14). Found (%): C,

K.-W. Chi et al. / Journal of Fluorine Chemistry 104 (2000) 263±271
271
13
1JCFˆ269.1), 118.1 (C , JCFˆ287.2; JCFˆ31.0), 115.4
2JCFˆ34.4), 109.5 (C4, 2JCFˆ10.1), 106.2 (C6,
F3), 41.4 (2F, F2), 18.5 (2F, F5), 7.6 (1F, F7), 0.2 (2F, F6).
HRMS calc. 328.9898 for C9HF10NO, found 328.9895.
1
2
(C4, JCFˆ256.8; JCFˆ32.3), 109.4 (C12, JCFˆ270.0;
2JCFˆ38.2), 46.0 (C14), 17.9 (C15). 19F NMR (CDCl3) dF
110.7 (3F, F11, m), 82.7 (3F, F13, s), 60.6 (2F, F12, q, 10),
37.2 (2F, F4, q, 10). IR 2935 (C±H); 1742 (C=C); 1652
(C=C); 1590 (C=N); 1476 (C±N), 1443 and 1410 (N±C);
1340, 1312, 1230±1190 (C±F) [23]. UV spectrum lmax
244 nm (eˆ14 300), 334 nm (eˆ1100). HRMS calc.
381.0575 for C14H9F10N, found 381.0561.
1JCFˆ266.4; JCFˆ39.0). 19F NMR (CDCl3) dF 80.6 (3F,
1
2
1
2
Acknowledgements
The authors are grateful to the Korea Research Founda-
tion and KISTEP in Korea for their ®nancial support for this
work.
3.2.13. Reaction of 1 with pentafluoroaniline
A mixture of 1 (10 g, 0.033 mol), penta¯uoroaniline
(6.1 g, 0.033 mol) and Et3N (6.7 g, 0.066 mol) in MeCN
(65 ml) was stirred at 458C for 3.5 h. The resulting solution
was neutralized with 5% aqueous H2SO4 and extracted with
CH2Cl2 (3 mlÂ50 ml). The concentrate was distilled under
reduced pressure to give a liquid fraction 1 (bp 45±558C
(4 Torr), 9.0 g) and fraction 2 (bp 118±1258C (9 Torr),
6.5 g). Fraction 1 was analyzed by 19F NMR and GC-MS
and consisted of 24 (21%), 23 (6%) and 22 (73%); fraction 2
was further puri®ed by column chromatography (hexane/
CH2Cl2) to provide 25.
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(Penta¯uorophenyl)-[3,3,3-tri¯uoro-1-(penta¯uoroethyl)-
2-tri¯uoromethylpropylidene]-amine (22): 3.5 g, bp 118±
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1JCFˆ253.9), 138.5 (C , JCFˆ252.8), 135.4 (C7), 135.4
8
1
(C9, JCFˆ249.9), 121.3 (C1,6
,
1JCFˆ282.3), 118.1 (C5,
1
[7] R.D. Chambers, C.R. Sargent, in: A.R. Katritzky, A.J. Boulton
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1JCFˆ286.3; 2JCFˆ34.0), 109.4 (C4, 1JCFˆ268.1;
2
2JCFˆ40.4), 51.8 (C , JCFˆ31.9). 19F NMR (CDCl3) dF
90.9 (6F, F1,6), 81.7 (3F, F5), 46.6 (F4), 12.2 (2F, F8), 2.7 (F,
F10), 0.1 (2F, F9). IR 1740 (C=C); 1710 (C=C); 1660 (C=N);
1615 (C=N), 1500 (C=Car), 1360 and 1340 (N±C); 1320,
1230±1160 (C±F) [23]. HRMS calc. 462.9853 for
C12HF16N, found 462.9847.
2
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[3,3-Di¯uoro-1-(penta¯uoroethyl)-2-tri¯uoromethyl-
allylidene]-(penta¯uorophenyl)-amine (23): bp 26±278C
(6 Torr). 19F NMR (CDCl3) dF 103.2 (1F, F1), 101.8 (3F,
F6), 91.4 (1F, F1), 83.5 (3F, F5), 50.5 (2F, F4), 14.8 (2F, F8),
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‡
‡
4.8 (F, F10), 0.1 (2F, F9). GC-MS 443 [M] , 424 [M±F] ,
‡
‡
‡
[15] G.G. Furin, V.A. Lopirev, E.L. Zhuzhgov, N.I. Prozuk, Zh. Org.
Khim. 36 (2000) 120.
324 [M±C2F5] , 312, 167 [C6F5] , 148 [C6F4] , 117
‡
‡
‡
[C5F3] , 93 [C3F3] , 69 [CF3] .
[16] G.G. Furin, V.G. Kiriyanko, E.L. Zhuzhgov, Zh. Org. Khim. 36
(2000) 33.
(Penta¯uorophenyl)-[2,2,3,3,3-penta¯uoro-1-(20,20,20-tri-
¯uoroethyl)-propylidene]-amine (24): bp 50±518C (6 Torr).
19F NMR (CDCl3) dF 102.4 (3F, F1), 82.8 (3F, F5), 51.8 (2F,
F4), 13.3 (2F, F7), 6.8 (2F, F9), 0.1 (2F, F8). GC-MS 395
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Chem. Commun. (1994) 134.
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31.
‡
‡
‡
‡
[M] , 376 [M±F] , 344 [M±CHF2] , 276 [M±C2F5] , 167
‡
‡
‡
‡
‡
[C6F5] , 148 [C6F4] , 117 [C5F3] , 93 [C3F3] , 69 [CF3] .
2,2,3,3,3-Penta¯uoro-N-(penta¯uorophenyl)-propiona-
mide (25): 6.5 g, mp 110±1128C (CH2Cl2). 1H NMR
(CDCl3) dH 5.46 (N±H). 13C NMR (CDCl3) dC 156.1
[22] Yu.V. Zeifman, L.S. German, Izv. Akad. Nauk, Ser. Khim. (1994)
1678.
(C1, JCFˆ27.2), 142.9 (C5, JCFˆ256.4; JCFˆ11.6),
140.4 (C7, 1JCFˆ254; 2JCFˆ13.7), 137.1 (C7,
1JCFˆ255.4; 2JCFˆ10.6), 117.1 (C3, 1JCFˆ286.2;
2
1
2
[23] L.L. Bellamy, The Infrared Spectra of Complex Molecules, Methuen
and Co., London; Wiley, New York, 1954, pp. 295±315.