Reactions of perfluoro(5-aza-4-nonene) with hydrazine and some its derivatives

Article abstract of DOI:10.1023/A:1013876707892

The reaction of perfluoro(5-aza-4-nonene) with hydrazine hydrate in tetrahydrofuran at 0-20°C in the presence of triethylamine yields 2,5-bis(heptafluoropropyl)-1H-1,2,4-triazole; under similar conditions perfluoro(5-aza-4-nonene) reacts with arylhydrazin

Full text of DOI:10.1023/A:1013876707892

Russian Journal of Organic Chemistry, Vol. 37, No. 11, 2001, pp. 1621 1628. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 11, 2001,
pp. 1693 1699.
Original Russian Text Copyright
2001 by Furin, Ki-Wan Chi, Protsuk, Lopyrev.
Reactions of Perfluoro(5-aza-4-nonene) with Hydrazine
and Some Its Derivatives
1
2
3
3
G. G. Furin , Ki-Wan Chi , N. I. Protsuk , and V. A. Lopyrev
1
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: benzol@nioch.nsc.ru
2
Ulsan University, South Korea
3
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
Received October 6, 2000
Abstract The reaction of perfluoro(5-aza-4-nonene) with hydrazine hydrate in tetrahydrofuran at 0 20 C
in the presence of triethylamine yields 2,5-bis(heptafluoropropyl)-1H-1,2,4-triazole; under similar conditions
perfluoro(5-aza-4-nonene) reacts with arylhydrazines to form 1-aryl-3,5-bis(heptafluoropropyl)-1,2,4-triazoles.
1
-Aryl-substituted azoles having perfluoroalkyl
afford 1-aryl-substituted pyrazole derivatives. The key
point of the process is formation of intermediates
containing a C C C N N conjugated bond
sequence. Intramolecular cyclization of such inter-
mediates leads to formation of five-membered hetero-
rings. While further developing the above approach,
the present work was aimed at finding an initial
fluorinated olefin whose reaction with arylhydrazines
would give an intermediate having a C N N N N
conjugated bond system. Our previous studies [14]
revealed that perfluoro(5-aza-4-nonene) (I) reacts with
aliphatic and aromatic amidines to form sym-triazine
groups attract interest as intermediate products in the
synthesis of potential biologically active compounds
which can be used in medicine and agriculture [1, 2].
As a rule, such products are obtained via introduction
of perfluoroalkyl groups into heteroring by various
methods [3, 4]. In the recent years, a new approach
was developed on the basis of reactions of com-
mercially available perfluoroolefins with difunctional
nucleophilic reagents [5 12]. We previously showed
[
13] that perfluoro(2-methyl-2-pentene) reacts with
arylhydrazines in the presence of triethylamine to
Scheme 1.
II, Ar =
; III, Ar =
; IV, Ar =
; V, Ar =
; VI, Ar =
; VII, Ar =
;
VIII, Ar =
; IX, Ar =
.
1
070-4280/01/3711-1621$25.00 2001 MAIK Nauka/Interperiodica

1
622
FURIN et al.
Scheme 2.
derivatives. We now focused on the reactions of I
with hydrazine hydrate and some its derivatives.
the N-propionyl group from intermediate XIV. No
dihydrazide formation was observed.
Perfluoro(5-aza-4-nonene) (I) reacted with aryl-
hydrazines in tetrahydrofuran in the presence of tri-
ethylamine under very mild conditions, yielding
By reaction of compound I with hydrazine hydrate
in acetic acid we obtained cyclization product XV
in 42% yield. A possible mechanism of this reaction
is shown in Scheme 4. Elimination of hydrogen
fluoride from the hydrazino group of primary adduct
XVI does not occur due to its high basicity, and com-
pound XVII is not formed. Instead, HF molecule is
released from the NH CF C F moiety to give
intermediate XVIII. Intramolecular cyclization of the
latter, followed by loss of two hydrogen fluoride
molecules (from intermediate D), leads to formation
of final product XV.
Perfluoro(2-methyl-2-pentene) (XIX) behaves like
compound I in reactions with 2,3,5,6-tetrafluoro-
phenylhydrazine, 4-bromo-2,3,5,6-tetrafluorophenyl-
hydrazine, and propionylhydrazine. The corresponding
pyrazole derivatives XX XXII were thus obtained
1
-aryl-3,5-bis(heptafluoropropyl)-1,2,4-triazoles II IX
(Scheme 1). Presumably, the final products are formed
as follows. Nucleophilic attack on compound I by
the NH group of pentafluorophenylhydrazine gives
2
intermediate X which is capable of losing hydrogen
fluoride by the action of triethylamine. Compound XI
could give rise to two processes. The first of these
includes replacement of fluorine at the C N bond
by hydrazino group and subsequent formation of bis-
hydrazone XII. The second pathway is intramolecular
nucleophilic cyclization with formation of 1,2,4-tri-
azole derivative V (Scheme 2). The nature of the aryl
group weakly affects the process. In the reaction with
2
3 7
4
,4 -dihydrazinooctafluorobiphenyl two triazole rings
were formed from the two hydrazine moieties
(
Scheme 5). On the other hand, the reaction of XIX
(compound IX).
with hydrazine hydrate under the same conditions
gave isomeric hydrazones XXIIIa and XXIIIb. Our
attempts to effect cyclization of compounds XXIIIa
and XXIIIb by the action of triethylamine in aceto-
nitrile resulted in formation of isomeric perfluoro-
Propionyl hydrazine reacted with flouoroolefin I
in the presence of triethylamine in acetonitrile to give
bis(heptafluoropropyl)-1H-1,2,4-triazole (XIII)
(Scheme 3), presumably as a result of elimination of
Scheme 3.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

REACTIONS OF PERFLUORO(5-AZA-4-NONENE) WITH HYDRAZINE
1623
Scheme 4.
Scheme 5.
XX, X = H; XXI, X = Br.
alkylcyclobutadienes XXIVa and XXIVb at a ratio
of 2.3:1 (yield 63%) instead of the expected pyrazole
derivatives (Scheme 6). Products XXIVa and XXIVb
are likely to be formed via dimerization of inter-
mediate alkyne XXV.
hexafluorobenzene were used as internal references
( C H coupling constants were not measured). The
IR spectra were obtained on a Specord M-80 instru-
1
3
1
ment in CCl . The mass spectra (70 eV) were run
4
on a VG 707 OE GC MS system. Perfluoro(5-aza-
4-nonene) (I) was synthesized by the procedure
described in [15].
EXPERIMENTAL
Typical procedure for synthesis of fluorinated
N-aryl-1,2,4-triazoles. A solution of 1 equiv of com-
pound I in 10 ml of THF was added over a period of
15 min to a solution of 1 equiv of arylhydrazine and
The H, 13C, and 19F NMR spectra were recorded
1
on a Bruker WP-400SY spectrometer at 400, 100, and
88 MHz, respectively; hexamethyldisiloxane and
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

1
624
FURIN et al.
Scheme 6.
1
3
at 0 C. The mixture was stirred for 1 h at 0 C, for
h at room temperature, and for 2 h at 50 C. It was
equiv of triethylamine in 40 ml of THF on stirring
7.71 (14-H). 3C NMR spectrum (CDCl3), , ppm:
C
3
2
5
2
1
3
(
54.5 (C , J
0.5 Hz), 159.9 (C ), 144.2 (C ), 134.7 (C ), 133.1
C ), 129.6 (C ), 126.1 (C ), 117.8 (C , J
= 30 Hz), 117.5 (C , J
JC, F = 29.6 Hz), 110.5 (C , J
8.7 Hz), 110.4 (C , J
08.6 (C , J = 266.9, J = 27.8 Hz), 108.4 (C ,
C, F C, F
JC, F = 268.7, J
CDCl3), F, ppm: 82.9 t (3F, 8-F, J = 9 Hz), 82.5 t
3F, 11-F, J = 9 Hz), 53.8 q (2F, 7-F, J = 9 Hz),
49.5 q (2F, 10-F, J 9 Hz), 37.6 s (2F, 6-F), 36.1 s (2F,
9-F). Mass spectrum, m/z (I , %): 526 (6) M , 507
= 29.6 Hz), 146.6 (C , J
=
C, F
C, F
2
12
13
14
then poured into 100 ml of water and extracted with
methylene chloride (3 70 ml). The extract was dried
over Na SO and evaporated, and the residue was
1
5
16
17
8
1
=
C, F
2
11
1
2
86.9, J
= 287.2,
C, F
C, F
2
4
2
6
1
2
distilled under reduced pressure or was subjected to
column chromatography using hexane methylene
chloride as eluent.
= 256.8, J
=
C, F
C, F
9
1
2
2
= 259.0, J
= 31 Hz),
C, F
C, F
7
1
2
10
1
3
,5-Bis(heptafluoropropyl)-1-phenyl-1,2,4-tri-
1
2
19
= 38.4 Hz). F NMR spectrum
C, F
azole (II) was synthesized from 2.48 g (23 mmol) of
phenylhydrazine and 9.96 g (23 mmol) of perfluoro-
(
(
olefin I. Yield 9.2 g (83%); yellow liquid, bp 81
1
8
(
2 C (0.3 mm). IR spectrum, , cm : 1658, 1520
+
1
rel
C N C C), 1338 (C N), 1236 1126 (C F). H
+
+
+
(
49) [M F] , 480 (2) [M NO ] , 457 (1) [M CF ] ,
407 (27) [M C F ] , 195 (1) [C F CN] , 169 (54)
2 3
NMR spectrum, , ppm: 7.26 (13-H), 7.36 (14-H),
+
+
1
3
2 5 3 7
7
1
3
(
1
.31 (15-H). C NMR spectrum (CDCl3), , ppm:
+
+
+
C
[
C F ] , 150 (4) [C H NO N ] , 119 (9) [C F ] ,
3
2
5
2
3 7 6 4 2 2 2 5
53.0 (C , J
0.1 Hz), 135.5 (C ), 130.1 (C ), 128.8 (C ), 125.0
C ), 117.0 (C , J
16.8 (C , J
= 267.5, J
JC, F = 267.7, J
= 31.6 Hz), 108.5 (C , J
JC, F = 31.7 Hz). F NMR spectrum, F, ppm: 82.5 t
= 29.5 Hz), 144.6 (C , J
=
+
+
C, F
C, F
118 (1) [C H NO ] , 106 (87) [C H NO] , 100 (5)
6 4 2 6 4
1
2
15
14
+
+
+
[
CF2 CF ] , 90 (32) [C H N] , 78 (100) [C H ] ,
2 6 4 6 6
1
3
8
1
2
+
+
+
= 276.8, J
= 34.4 Hz),
76 (17) [C H ] , 69 (50) [CF ] , 46 (1) [NO ] .
C, F
C, F
6 4 3 2
1
1
1
2
= 276.2, J
= 34.5 Hz), 106.7
= 34.4 Hz), 106.3 (C ,
= 34.2 Hz), 108.9 (C , J
Found: M 526.0124. C H F N O . Calculated:
14 4 14 4 2
C, F
C, F
7
1
2
10
M 526.0110.
(
C , J
C, F
C, F
1
2
6
1
1-(2,4-Dinitrophenyl)-3,5-bis(heptafluoropropyl)-
1,2,4-triazole (IV) was synthesized from 5.03 g
25 mmol) of 2,4-dinitrophenylhydrazine and 10.8 g
(25 mmol) of compound I. Yield 7.5 g (53%); brown
=
C, F
C, F
9
1
2
58.8, 2J
= 258.5,
C, F
C, F
(
2
19
(
5
9
3F, 11-F, J = 9 Hz), 83.8 t (3F, 8-F, J = 9 Hz),
3.0 q (2F, 7-F, J = 9 Hz), 50.0 q (2F, 10-F, J =
liquid, bp 104 106 C (0.3 mm). UV spectrum
1
1
(C H OH),
3
, nm ( , l mol cm ): 228 (11800),
2
5
max
Hz), 38.2 s (2F, 6-F), 36.4 s (2F, 9-F). Mass spec-
1
34 (850). IR spectrum, , cm : 1590, 1545
(C Carom); 1610, 1520 (C C C N); 1540 (NO2,
asym.); 1350 (NO , sym.); 1320 (C N); 1220 1150
(C F). H NMR spectrum, , ppm: 9.15 d (14-H,
J = 2.5 Hz), 8.78 d.d (17-H, J = 8, 2.5 Hz), 8.02 d
(16-H, J = 8 Hz). C NMR spectrum (CDCl ), C,
ppm: 155.1 (C , J
0 Hz), 145.0 (C ), 134 (C , C ), 129.1 (C ),
29.0 (C ), 122 (C ), 117.3 (C , J
JC, F = 32.8 Hz), 117.6 (C , J
33.1 Hz), 108.2 (C , J
08.3 (C , J
(C , JC, F = 262.4, JC, F = 31.2 Hz), 110.2 (C ,
JC, F = 257.4, J
+
+
trum, m/z (I , %): 481 (73) M , 462 (20) [M F] ,
3
rel
+
+
62 (51) [M C F ] , 262 (2) [M 2C F ] , 169 (2)
2 5 2 5
+
+
+
2
1
[
(
C F ] , 119 (5) [C F ] , 91 (100) [C H N] , 77
3 7 2 5 6 5
+
+
18) [C H ] , 69 (6) [CF ] . Found: M 481.0245.
6
5
3
1
3
C H F N . Calculated: M 481.0259.
1
4
5
14
3
3
3
2
5 2
3
,5-Bis(heptafluoropropyl)-1-(2-nitrophenyl)-
= 31 Hz), 146.7 (C , J
=
C, F
12
C, F
16
1
,2,4-triazole (III) was synthesized from 5.2 g
13
15
3
(
(
34 mmol) of 2-nitrophenylhydrazine and 14.7 g
34 mmol) of compound I. Yield 14.8 g (83%);
14
17
8
1
1
= 288.1,
C, F
2
11
1
2
= 287.3, J
=
C, F
C, F
yellow liquid, bp 150 151 C (0.5 mm). IR spectrum,
7
1
2
1
= 263.4, J = 39.5 Hz),
,
cm : 1610, 1590, 1545 (C Carom); 1520
C C C N); 1540 (NO , asym.); 1350 (NO , sym.);
1
C, F C, F
1
0
1
2
1
= 264.3, J
= 34.6 Hz), 110.1
(
C, F
C, F
2
2
1
6
1
2
7
320 (C N); 1220 1150 (C F). H NMR spectrum
1
2
19
(
CDCl3), , ppm: 8.31 (17-H), 7.88 (15-H, 16-H),
= 31.2 Hz). F NMR spectrum
C, F
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

REACTIONS OF PERFLUORO(5-AZA-4-NONENE) WITH HYDRAZINE
1625
2
11 1
(
(
4
CDCl3), F, ppm: 82.9 t (3F, 8-F, J = 9 Hz), 82.5 t
3F, 11-F, J = 9 Hz), 54.0 q (2F, 7-F, J = 9 Hz),
1J
= 259.2, J
= 15.9 Hz), 118.3 (C , J
=
C, F
C, F
C, F
2
8
1
2
J
85.7, J
= 33.2 Hz), 117.9 (C , J
= 33.5 Hz), 110.3 (C , J = 14.2 Hz), 110.2
= 283.5,
C, F
C, F
9.2 q (2F, 10-F, J = 9 Hz), 37.7 s (2F, 6-F), 36.0 s
2
12 2
+
C, F
C, F
(
2F, 9-F). Mass spectrum, m/z (I , %): 571 (3) M ,
rel
9
1
2
6
+
+
(C , J
= 258.5, J
= 32.1 Hz), 109.5 (C ,
C, F
C, F
5
52 (42) [M F] , 452 (37) [M C F ] , 404 (2)
2 5
1
2
10 1
+
+
JC, F = 257.9, J
= 34.1 Hz), 108.9 (C , J
=
[M C H (NO ) ] , 376 (36) [M C F CN] , 348 (17)
C, F
C, F
6
3
2 2
3 7
+
+
2
7
1
[
[
C F CN, N ] , 195 (1) [C F CN] , 181 (4)
267.4, JC, F = 34.1 Hz), 108.3 (C , JC, F = 268,
JC, F = 33.9 Hz). F NMR spectrum (CDCl3), F,
ppm: 83.4 s (3F, 11-F), 83.0 s (3F, 8-F), 52.3 m (2F,
10-F), 49.8 m (2F, 7-F), 37.8 m (2F, 9-F), 36.7 m
3
7
2
3 7
+
+
2
19
C H (NO ) N] , 169 (100) [C F ] , 145 (2)
6
3
2 2
3 7
+
+
+
[C F CN] , 119 (11) [C F ] , 100 (9) [CF CF ] ,
2
5
2
5
2
2
+
6
9 (49) [CF ] . Found, %: C 29.42; H 0.53; F 46.58;
3
N 12.26. M 570.9953. C H F N O . Calculated, %:
C 29.34; H 0.45; F 46.68; N 12.47. M 570.9961.
(2F, 6-F), 27.1 m (2F, 13-F), 18.3 m (1F, 15-F). Mass
1
4
3
14
5
4
+
spectrum, m/z (I , %): 553 (50) M , 534 (32)
rel
+
+
[
M F] , 434 (78) [M C F ] , 239 (0.9) [M
C F CN C F ] , 215 (0.7) [HC F N C ] , 177
(2) [HC F N ] , 163 (100) [HC F N] , 149 (12)
6 4 2 6 4
Perfluoro(3,5-dipropyl-1-phenyl-1,2,4-triazole)
2 5
+
+
(V) was synthesized from 4.95 g (25 mmol) of penta-
3
7
2
5
6
4
3
2
+
+
fluorophenylhydrazine and 10.8 g (25 mmol) of com-
pound I. Yield 12.8 g (90%); yellow liquid, bp 71
+
+
+
[HC F ] , 119 (4) [C F ] , 100 (3) [CF CF ] , 69
6 4 2 5 2 2
+
7
2 C (3 mm). UV spectrum (C H OH),
, nm ( ,
(22) [CF ] . Found: M 552.9873. C HF N . Cal-
2
5
max
3
14
18
3
1
1
l mol cm): 265 (900). IR spectrum, , cm : 1527
culated: M 552.9883.
(
(
C C), 1520 (C N), 1338 (C N), 1236 1126
1-(4-Bromo-2,3,5,6-tetrafluorophenyl)-3,5-bis-
(heptafluoropropyl)-1,2,4-triazole (VII) was syn-
thesized from 2.59 g (10 mmol) of 4-bromo-2,3,5,6-
tetrafluorophenylhydrazine, 4.33 g (10 mmol) of com-
pound I, and 2.02 g (20 mmol) of triethylamine. Yield
1
3
C F). C NMR spectrum (CDCl ), C, ppm: 155.9
3
3
2
5
2
(C , J
= 30.0 Hz), 147.9 (C , J
= 253.9 Hz), 144 (C , J
58.7 Hz), 138.3 (C , J = 258.2 Hz), 117.9 (C ,
C, F
= 30.9 Hz),
C, F
C, F
1
5
1
13
1
1
44.4 (C , J
=
C, F
C, F
1
4
1
11
2
3
.6 g (57%); yellow liquid, bp 90 91 C (2 mm). UV
1
2
8
1
JC, F = 261.7, J
= 33.2 Hz), 117.4 (C , J
=
1
1
C, F
C, F
spectrum (EtOH),
, nm ( , l mol cm ): 250
53.5, 2J = 33.5 Hz), 111.5 (C , J = 35.8 Hz),
12
2
max
2
1
C, F
C, F
(3500). IR spectrum, , cm : 1711 (C C), 1673
9
1
2
6
1
10.2 (C , J = 258.5, J = 32.1 Hz), 109.5 (C ,
C, F C, F
(C N), 1527 and 1508 (C C ), 1404 and 1338
arom
1
2
10 1
1
3
JC, F = 257.9, J
67.4, 2J
= 34.1 Hz), 108.9 (C , J
= 34.1 Hz), 108.3 (C , J
=
C, F
C, F
(C N), 1229 1158 (C F). C NMR spectrum
7
1
3 2
2
= 268,
(CDCl ), , ppm: 161.4 (C , J = 24.6 Hz), 159.1
C, F
C, F
3
C
C, F
15
2
19
5
2
2
JC, F = 33.9 Hz). F NMR spectrum (CDCl3), F,
ppm: 83.5 s (3F, 11-F), 83.1 s (3F, 8-F), 52.6 m (2F,
(C , J
= 26.0 Hz), 155.1 (C , J
= 25.3 Hz),
C, F
C, F
13
1
2
1
44.8 (C , J
= 246.7, J
= 15.7 Hz), 142.8
C, F
C, F
1
6
0-F), 49.7 m (2F, 7-F), 38 m (2F, 9-F), 36.8 m (2F,
14
1
2
11
(
C , J
= 257.2, J
= 15.9 Hz), 118.4 (C ,
C, F
C, F
-F), 19.3 m (2F, 13-F), 16.6 m (1F, 15-F), 3.4 m
1
2
8
1
+
JC, F = 285.1, J
= 33.8 Hz), 117.9 (C , J
C, F
=
(
[
[
2F, 14-F). Mass spectrum, m/z (I , %): 571 M , 552
C, F
rel
2
83.5, 2J = 33.5 Hz), 110.3 (C , J = 13.8 Hz),
12
2
+
+
+
M F] , 452 [M C F ] , 376 [M C F CN] , 357
M C F CF C N] , 257, 224, 169 [C F ] , 167
C, F
C, F
2
5
3 7
+
+
9
1
2
6
110.2 (C , J = 258.5, J = 32.1 Hz), 109.5 (C ,
2
+
5
3
7
C, F
C, F
+
+
1
2
10 1
[C F ] , 119 [C F ] , 69 [CF ] . Found: M 570.97830.
JC, F 257.5, J 34.0 Hz), 108.9 (C , J = 267.4,
6
5
2
5
3
C, F
C, F
2J
= 34.1 Hz), 108.3 (C , J
7
1
= 268, J
2
=
C F N . Calculated: M 570.97886.
1
4
19
3
C, F
C, F
C, F
1
9
3,5-Bis(heptafluoropropyl)-1-(2,3,5,6-tetrafluoro-
33.9 Hz). F NMR spectrum (CDCl3), F, ppm:
82.8 s (3F, 11-F), 82.8 s (3F, 8-F), 52.2 m (2F, 10-F),
46.8 m (2F, 7-F), 37.8 m (2F, 9-F), 37.7 m (2F, 6-F),
18.8 m (2F, 13-F), 33.3 m (1F, 15-F). Mass spectrum,
m/z (I , %): 631 (53) M , 612 (20) [M F] , 512 (40)
[M C F ] , 256 (4) [BrC F N ] , 241 (44)
phenyl)-1,2,4-triazole (VI) was synthesized from
1
4
.8 g (10 mmol) of 2,3,5,6-tetrafluorophenylhydrazine,
.33 g (10 mmol) of compound I, and 2.02 g
+
+
(20 mmol) of triethylamine. Yield 4 g (72%); yellow
rel
+
+
liquid, bp 134 135 C (3 mm). UV spectrum (EtOH),
2
5
6
+
4
3
1
1
max, nm ( , l mol cm ): 271 (2700). IR spectrum,
+
+
[BrC F NH] , 229 (4) [BrC F ] , 169 (12) [C F ] ,
1
6
4
6
4
3 7
,
cm : 3086 (C N), 1650 (C C), 1631 (C N),
+
+
1
48 (9) [C F ] , 119 (10) [C F ] , 100 (5)
6 4 2 5
1
531 and 1508 (C Carom), 1345 (C N), 1236 1187
+
+
[CF2 CF ] , 69 (50) [CF ] . Found: M 630.9396.
1
2
3
(C F). H NMR spectrum, , ppm: 7.47 (Harom).
C BrF N . Calculated: M 630.8988.
1
4
18
3
1
3
3
C NMR spectrum (CDCl ),
, ppm: 156.1 (C ,
3
C
3,5-Bis(heptafluoropropyl)-1-(2,3,5,6-tetrafluoro-
4-trifluoromethylphenyl)-1,2,4-triazole (VIII) was
synthesized from 6.2 g (25 mmol) of 2,3,5,6-tetra-
2J
= 30.1 Hz), 148.1 (C , J = 26.4 Hz), 146.3
C, F
15
2
C, F
1
3
1
2
14
(C , J
= 252.7, J
= 15.7 Hz), 143.5 (C ,
C, F
C, F
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

1
626
FURIN et al.
fluoro-4-trifluoromethylphenylhydrazine and 10.8 g
25 mmol) of compound I. Yield 13 g (84%); yellow
liquid, bp 80 81 C (3 mm). UV spectrum (EtOH),
Yield 3.5 g (83%); slightly yellowish liquid, bp 69
70 C. IR spectrum, , cm : 3084 (C N), 1620
1
(
(C C), 1527 (C Carom), 1471 and 1887 (C N),
1
1
1
max, nm ( , l mol cm ): 282 (2300). IR spectrum,
1225 1160 (C F). H NMR spectrum, , ppm: 7.44.
1
13
3
,
cm : 1658 (C C), 1514 (C N), 1510 (C Carom),
C NMR spectrum (CDCl ),
, ppm: 141.0 (C ,
3
C
1
3
2J
11
1
2
1
(
(
1
340 (C N), 1220 1124 (C F). C NMR spectrum
= 31.5 Hz), 146.7 (C , J
= 257.3, J
=
C, F
C, F
C, F
3
2
1
0
1
2
CDCl ), , ppm: 156.9 (C , J = 30.3 Hz), 148.3
3 C
C, F
14 1
13.5 Hz), 143.4 (C , J = 258.8, J = 15.5 Hz),
C, F C, F
5
2
6
1
8 1
C , J
= 31.2 Hz), 145 (C , J
= 269.4 Hz),
C, F
C, F
120 (C , J = 267.8 Hz), 118.7 (C , J = 286.3,
C, F C, F
1
3
1
15
2
2
9 2
44.1 (C , J
2 Hz), 120.7 (C , J
JC, F = 286.8, J
86.2, 2J
JC, F = 40.2 Hz), 110.6 (C , J
9.2 Hz), 108.9 (C , J = 267.0, J = 38.6 Hz),
C, F C, F
08.8 (C , J
= 261.9 Hz), 136.2 (C , J
=
C, F
C, F
J
= 41.4 Hz), 110.3 (C , J
= 13.4 Hz), 109.4
C, F
C, F
1
6
1
11
7
1
2
12
3
= 275.5 Hz), 118.2 (C ,
= 33.4 Hz), 117.8 (C , J
C, F
(C , J
= 253.8, J
= 40.3 Hz), 109.4 (C ,
C, F
C, F
1
2
8
1
2
4
2
2
=
C, F
C, F
JC, F = 15.5 Hz), 96.0 (C , J
= 34.3, J
=
C, F
C, F
9
1
8.5 Hz). 19F NMR spectrum (CDCl3), F, ppm:
2
= 33.5 Hz), 110.7 (C , J
= 259.5,
C, F
C, F
2
6
1
2
= 257.7, J
=
107.1 d.t (6-F, J = 22, 7 Hz), 80.2 s (8-F), 51.8 q
C, F
C, F
1
0
1
2
(
7-F, J = 7 Hz), 43.4 q (5-F, J = 22 Hz), 27.1 m
3
1
7
1
2
19
(11-F), 17.4 m (10-F). Mass spectrum, m/z (I , %):
4
3
rel
= 268.5, J = 39.7 Hz). F NMR
C, F
C, F
+
+
+
20 (59) M , 401 (29) [M F] , 351 (100) [M CF ] ,
01 (8) [M C F ] , 282 (10) [M F C F ] , 263 (5)
3
spectrum (CDCl3), F, ppm: 106.8 s (3F, 16-F), 83.5 s
3F, 11-F), 83.1 s (3F, 8-F), 52.5 m (2F, 10-F),
+
+
2
5
2 5
(
+
+
[
M 2F C F ] , 256 (8) [M HC F N] , 232 (0.7)
2 5 6 4
4
2
9.7 m (2F, 7-F), 38 m (2F, 9-F), 36.8 m (2F, 6-F),
6.2 m (2F, 13-F), 21.3 m (2F, 14-F). Mass spectrum,
+
+
[M CF3 C F ] , 207 (0.4) [M HC F NCF ] , 176
2
5
6
4
2
+
+
+
+
+
+
(7) [C F N ] , 149 (12) [HC F ] , 119 (3) [C F ] ,
100 (2) [CF2 CF ] , 69 (28) [CF ] . Found: M
2 3
6 4 2 6 4 2 5
m/z (I , %): 621 M , 602 [M F] , 502 [M C F ] ,
rel
2
5
+
+
+
+
4
3
26 [M C F CN] , 407 [M C F CF C N] ,
3 7 2 5
+
+
419.9967. C HF N . Calculated: M 419.9932.
12 13 2
06, 231, 216, 169 [C F ] , 69 [CF ] . Found:
3
7
3
1
-(4-Bromo-2,3,5,6-tetrafluorophenyl)-5-fluoro-
-pentafluoroethyl-4-trifluoromethyl-1H-pyrazole
XXI) was synthesized from 3 g (10 mmol) of com-
M 620.97550. C F N . Calculated: M 620.97567.
1
5
21
3
3
4
,4 -Bis[3,5-bis(heptafluoropropyl)-1,2,4-triazol-
(
1
-yl]octafluorobiphenyl (IX) was synthesized from
pound XIX, 2.59 g (10 mmol) of 4-bromo-2,3,5,6-
tetrafluorophenylhydrazine, and 3.03 g (30 mmol) of
triethylamine. Liquid substance, bp 84 85 C (2 mm).
4
.1 g (11.5 mmol) of 4,4 -dihydrazinooctafluorobi-
phenyl and 10 g (23 mmol) of compound I. Yield
5
.4 g (42%); yellow liquid, bp 163 164 C (0.2 mm).
1
1
1
IR spectrum, , cm : 1623 (C C), 1539 (C N),
UV spectrum (EtOH),
, nm ( , l mol cm ): 240
max
1
503 (C Carom), 1357 and 1328 (C N), 1225 1162
1
3
(8200), 280 (1750). C NMR spectrum (CDCl ), C,
3
13
(C F). C NMR spectrum (CDCl ), C, ppm: 152.3
3
2
5
2
3
ppm: 156.9 (C , J
3
1
= 30.2 Hz), 148.5 (C , J
0.9 Hz), 144.9 (C , J = 251.9, J = 12.5 Hz),
C, F C, F
=
C, F
C, F
5
1
3 2
1
3
1
2
(C , JC, F = 298.8 Hz), 141.3 (C , JC, F = 39.6 Hz),
145.7 (C , J
11
1
2
1
4
1
2
= 255.3, J
= 13.5 Hz), 144.4
C, F
C, F
44.1 (C , J
= 261.7, J
= 12.5 Hz), 118.8
C, F
C, F
10
1
2
6
1
2
2
8
1
(C , J
= 263.3, J
= 15.5 Hz), 119.6 (C ,
C, F
C, F
(
C , J
= 24.4 Hz), 118.5 (C , J
= 286.8,
= 287.1, J
= 24.6 Hz), 110.5 (C ,
= 31.3 Hz), 110.4 (C , J
C, F
C, F
1
8
1
2
2
11
1
2
JC, F = 272.8 Hz), 118.2 (C , J
= 286.1, J
=
C, F
C, F
JC, F = 33.2 Hz), 118.1 (C , J
=
C, F
C, F
1
2
2
7
1
5
2
6
36.4 Hz), 115.8 (C , J
= 15.5 Hz), 109.7 (C ,
3
3.1 Hz), 110.7 (C , J
C, F
C, F
1
2
9
2
1
2
9
1
JC, F = 267.9, J
= 40.3 Hz), 104.5 (C , J
=
JC, F = 256.8, J
=
C, F
C, F
C, F
C, F
2
7
1
4
2
2
2
59.0, J
= 31 Hz), 108.9 (C , J
= 268.9,
= 268.7, J
22.5 Hz), 95.4 (C , J
= 34.3, J
= 8.5 Hz).
C, F
C, F
C, F
C, F
2
10
1
2
19
JC, F = 32.9 Hz), 108.4 (C , J
=
F NMR spectrum (CDCl3), F, ppm: 106.7 d.t (6-F,
C, F
C, F
3
8
0.4 Hz). 19F NMR spectrum (CDCl3), F, ppm:
J = 22, 7 Hz), 80.4 s (8-F), 51.4 q (7-F, J = 7 Hz),
3.5 t (8-F, J = 9 Hz), 83.1 t (11-F, J = 9 Hz), 52.5 q
44.1 q (5-F, J = 22 Hz), 32.9 m (11-F), 18.7 m (10-F).
+
(
7-F, J = 9 Hz), 49.7 q (10-F, J = 9 Hz), 37.9 s (6-F),
6.6 s (9-F), 29.1 m (14-F), 19.9 m (13-F). Found, %:
C 30.65; F 61.85; N 7.30. C F N . Calculated, %:
Mass spectrum, m/z (I , %): 498 (100) M , 479 (32)
rel
+
+
+
3
[M F] , 429 (93) [M CF ] , 256 (2) [BrC F N ] ,
3 6 4 2
+
+
228 (1) [BrC F ] , 119 (14) [C F ] , 100 (3)
2
8
36
6
6
4
2 5
+
+
C 30.43; F 61.96; N 7.61.
[CF2 CF ] , 69 (66) [CF ] . Found: M 497.9028.
2 3
C BrF N . Calculated: M 497.9038.
5
-Fluoro-3-(pentafluoroethyl)-1-(2,3,5,6-tetra-
12
13
2
fluorophenyl)-4-trifluoromethyl-1H-pyrazole (XX)
was synthesized from 3 g (10 mmol) of compound
XIX, 1.8 g (10 mmol) of 2,3,5,6-tetrafluorophenyl-
hydrazine, and 3.03 g (30 mmol) of triethylamine.
Reactions of compounds I and XIX with hydra-
zine hydrate (general procedure). Hydrazine hydrate,
2 equiv, was added at 0 C to a solution of compound
I or XIX in 35 ml of acetic acid. The mixture was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

REACTIONS OF PERFLUORO(5-AZA-4-NONENE) WITH HYDRAZINE
1627
stirred for 1 h at that temperature, heated for 2 h at
5 C, cooled, poured into 100 ml of water, and treated
with methylene chloride (3 70 ml). The extract was
washed with water (2 50 ml), dried over MgSO4,
and evaporated, and the residue was distilled or
(CDCl3), F, ppm: 102.2 (6F, 1-F, 6-F), 82.0 (3F,
5-F), 52.3 (2F, 4-F).
4
1
Isomer XXIIIb. H NMR spectrum, , ppm: 3.67
1
3
(CH), 6.10 (NH ). C NMR spectrum (CDCl ),
,
2
3
C
3
2
1
6
ppm: 165.4 (C , J
= 26.8 Hz), 113.6 (C , C ,
C, F
subjected to column chromatography on silica gel
using hexane methylene chloride as eluent.
1
5
1
2
JC, F = 282.1 Hz), 110.1 (C , J
= 282.9, J
=
C, F
C, F
4
1
2
3
6.6 Hz), 103.6 (C , J
= 260.5, J = 34.7 Hz),
C, F
C, F
3
,5-Bis(heptafluoropropyl)-4H-1,2,4-triazole
2
2
19
3
5.6 (C , J
= 31.2 Hz). F NMR spectrum
C, F
(XV) was synthesized from 17 g (39 mmol) of per-
(
4
CDCl3), F, ppm: 98.3 (6F, 1-F), 79.8 (3F, 5-F),
6.7 (2F, 4-F).
fluoro(5-aza-4-nonene) (I) and 3.9 g (78 mmol). of
hydrazine hydrate. Yield 6.7 g (42%), mp 96 98 C.
1
1
Bis(trifluoromethyl)bis[2,2,2-trifluoro-1-(tri-
UV spectrum (EtOH),
(
(
, nm ( , l mol cm ): 334
max
1
fluoromethyl)ethyl]cyclobutadienes XXIVa and
XXIVb. A mixture of 6.5 g (21 mmol) of compounds
XXIIIa/XXIIIb and 4.2 g (42 mmol) of triethylamine
in 30 ml of acetonitrile was stirred for 3 h at 80 C.
It was then poured into 100 ml of water and treated
with methylene chloride (3 70 ml). The extract was
washed with water (2 50 ml) and dried over Na SO .
4200). IR spectrum, , cm : 1620 (C N), 1450
C N), 1350 (C N), 1120 1220 (C F). H NMR
spectrum, , ppm: 8.17 (NH). C NMR spectrum
1
1
3
3
5 2
(
1
CDCl3), , ppm: 158.7 (C , C , J
= 25.7 Hz),
C
C, F
8
11
1
2
17.3 (C , C , J = 287.3, J = 33.5 Hz), 110.2
C, F C, F
6
9
1
2
7
(C , C , J
= 264.4, J
= 31.4 Hz), 108.0 (C ,
= 31.8 Hz). F NMR spec-
C, F
C, F
2
4
1
0
1
2
19
Removal of the solvent, followed by distillation, gave
.2 g (63%) of a mixture of compounds XXIVa and
C , J
= 255.5, J
C, F
C, F
3
trum (CDCl3), F, ppm: 82.97 (6F, 8-F, 11-F), 50.69
4F, 7-F, 10-F), 36.8 (4F, 6-F, 9-F). Mass spectrum,
XXIVb (ratio 2.3:1, according to the GLC data) as
(
+
+
a volatile mobile liquid, bp 80 82 C. Mass spectrum,
m/z (I , %): 405 (1) M , 386 (26) [M F] , 336 (1)
[
C F ] , 196 (1) [C F C NH] , 169 (5) [C F ] ,
1
rel
+
+
+
+
m/z (I , %): 488 (17) M , 469 (28) [M F] , 419 (8)
M CF ] , 286 (100) [M C F ] , 236 (1) [M
rel
3
2
5
+
+
[
M CF ] , 400 (10) [M CF F] , 337 (2) [M
3 3
CH(CF ) ] , 268 (1) [M CF CH(CF ) ] , 244 (1)
+
+
+
+
+
3
7
3
7
3 7
+
+
3 2
3
3 2
19 (5) [C F ] , 76 (1) [CF C N] , 69 (33)
+
+
2
5
2
[
[
(
(CF ) CHCCCF ] , 151 (1) [(CF ) CH] , 119 (7)
+
3 2 3 3 2
[
CF ] . Found: M 404.9859. C HF N . Calculated:
3 8 14 3
+
+
+
C F ] , 100 (1) [CF CF ] , 82 (1) [CF CH] , 69
2 5 2 2 3
83) [CF ] , 41 (100), 40 (49), 39 (16). Found:
M 404.9834.
+
3
3
,3,3-Trifluoro-1-pentafluoroethyl-2-trifluoro-
M 487.9846. C H F . Calculated: M 487.9869.
1
2
2 18
methylpropylidenehydrazine XXIIIa/XXIIIb. By
the above procedure, from 9 g (30 mmol) of com-
pound XIX and 3 g (60 mmol) of hydrazine hydrate
we obtained a mixture of isomeric hydrazones XXIIIa
and XXIIIb at a ratio of 2.1:1 (GLC) as a yellow
1
3
Isomer XXIVa. C NMR spectrum (CDCl ), C,
3
2
4
7
8
11
12 1
ppm: 129.5 (C , C ), 120.3 (C , C , C , C , J
=
C, F
5
9
1
282.6 Hz), 119.8 (C , C , J
= 269.8 Hz), 113.2
C, F
1
3
2
6
10
2
(C , C , J
2
= 37.8 Hz), 46.6 (C , C , J
=
C, F
C, F
liquid, bp 128 129 C. Yield 5 g (53%). IR spectrum,
19
2.5 Hz). F NMR spectrum (CDCl3), F, ppm: 102.9
1
,
cm : 3400, 3500 (NH ); 2990 (C H); 1710
(6F, 5-F, 9-F), 96.8 (12F, 7-F, 8-F, 11-F, 12-F).
2
(
(
2
[
[
[
C N); 1600 (C N); 1380, 1350 (C N); 1280 1150
13
Isomer XXIVb. C NMR spectrum (CDCl ), C,
+
3
C F). Mass spectrum, m/z (I , %): 312 (68) M ,
rel
8
9
11
12
1
+
+
ppm: 120.4 (C , C , C , C , J
= 283.2 Hz),
C, F
93 (17) [M F] , 273 (6) [M F HF] , 243 (5)
M CF ] , 193 (100) [M C F ] , 161 (23)
C F C NNH ] , 119 (11) [C F ] , 100 (1)
CF2 CF ] , 69 (28) [CF ] , 42 (1) [H NN C] .
5
6
1
3
4
+
+
119.9 (C , C , J
= 270.3 Hz), 129.6 (C , C ),
C, F
3
2 5
+
+
1
2
2
7
10 2
114.2 (C , C , JC, F = 38.0 Hz), 46.9 (C , C , JC, F =
22.5 Hz). F NMR spectrum (CDCl3), F, ppm: 100.5
2
5
2
2 5
+
+
+
19
2
3
2
Found, %: C 24.77; H 1.04; F 67.18; N 8.50.
M 312.0127. C H F N . Calculated, %: C 23.08;
(12F, 8-F, 9-F, 11-F, 12-F), 103.5 (6F, 5-F, 6-F).
6
3
11
2
5-Fluoro-3-pentafluoroethyl-4-trifluoromethyl-
H-pyrazole (XXII). A solution of 15 g (50 mmol)
H 0.96; F 66.99; N 8.97. M 312.0121.
1
1
Isomer XXIIIa. H NMR spectrum, , ppm: 3.67
of compound XIX and 10.1 g (100 mmol) of triethyl-
amine in 40 ml of acetonitrile was stirred for 2 h at
40 C. It was then cooled to 0 C, and 5.1 g (50 mmol)
of propionylhydrazine was added over a period of
1
3
(
CH), 6.30 (NH ). C NMR spectrum (CDCl ),
,
2
3
3
1
C
2
6
ppm: 165.8 (C , J
= 27.0 Hz), 113.7 (C , C ,
C, F
1
5
1
2
JC, F = 282.1 Hz), 110.4 (C , J
= 288.1, J
=
C, F
C, F
1
5 min, maintaining the temperature at 0 C. The mix-
4
1
2
3
3
6.4 Hz), 101.8 (C , J
= 260.8, J = 41.8 Hz),
C, F
C, F
ture was stirred for 1 h at 0 C and for 3 h at 40 C,
20 ml of DMF was added, and the mixture was heated
2
2
19
8.0 (C , JC, F = 32.5 Hz). F NMR spectrum
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

1
628
FURIN et al.
for 1 h at 40 C, cooled, poured into 100 ml of water,
and extracted with methylene chloride (3 70 ml).
The extract was washed with water (2 50 ml), dried
2. Ritter, S.K. and Washington, C., Chem. Eng. News,
1995, vol. 73, pp. 39 44.
3
4
5
.
.
.
Synthetic Fluorine Chemistry, Olah, G.A., Cham-
bers, R.D., and Prakash, G.K.S., Eds., New York:
Wiley, 1992; Tozer, M.J. and Herpin, T.F., Tetra-
hedron, 1996, vol. 52, no. 26, pp. 8619 8683.
over MgSO , and evaporated, and the residue was
4
distilled under reduced pressure. Yield 9.1 g (67%);
yellow liquid, bp 60 61 C (0.6 mm). IR spectrum, ,
1
cm : 3400 (NH); 1670 (C N); 1500 (C N); 1330,
Organofluorine Compounds in Medicinal Chemistry
and Biomedical Applications, Filler, R., Koba-
yashi, Y., and Yagupolskii, L.M., Eds., Amsterdam:
Elsevier, 1993.
1
1
,
380 (C N); 1140 1220 (C F). H NMR spectrum,
1
3
ppm: 8.24 (NH). C NMR spectrum (CD Cl ), C,
ppm: 150.3 (C , J = 259.0 Hz), 122.6 (C , J
2 2
5
1
3 2
=
C, F
C, F
6
1
2
Bargamova, M.D., Karpavichyus, K.I., Belostots-
kii, A.M., Motsshikite, S.M., and Knunyants, I.L.,
USSR Inventor’s Certificate no. 1456419, 1989;
Chem. Abstr., 1989, vol. 111, no. 97232y.
3
1.9 Hz), 112.1 (C , J
= 266.6, J
= 5 Hz),
C, F
C, F
8
1
= 285.9, 2J
7
1
1
09.6 (C , J
= 37.5 Hz), 100.8 (C ,
JC, F = 254.9, 2J = 40.7 Hz), 86.9 (C , J = 41.6,
C, F
C, F
4 2
C, F
C, F
2J
= 17.1 Hz). F NMR spectrum (CD Cl ), F,
19
C, F
2 2
6. Bargamov, G.G., Mysov, E.I., and Bargamova, M.D.,
Izv. Ross. Akad. Nauk, Ser. Khim., 1994, no. 11,
pp. 2039 2040.
ppm: 108.1 d.t (3F, 6-F, J = 20, 10 Hz), 79.2 s (3F,
-F), 51.10 q (2F, 7-F, J = 10 Hz), 36.1 q (1F, 5-F,
J = 20 Hz). Mass spectrum, m/z (I , %): 272 (47)
8
rel
7. Bargamova, M.D. and German, L.S., Izv. Akad.
Nauk SSSR, Ser. Khim., 1991, no. 6, pp. 1463 1464.
+
+
+
M , 253 (44) [M F] , 243 (1) [M N H] , 203
100) [M CF ] , 183 (42) [M CF HF] , 155 (12)
2
+
+
(
[
[
3 3
8. Bargamova, M.D., Motsshikite, S.M., and
Knunyants, I.L., USSR Inventor’s Certificate
no. 1456418, 1987; Byull. Izobret., no. 5, p. 80.
+
+
M CF3 HF N ] , 119 (12) [C F ] , 69 (58)
2
2 5
+
CF ] . Found, %: C 26.40; H 0.29; F 69.15; N 10.15.
3
C HF N . Calculated, %: C 26.47; H 0.37; F 68.87;
6
9
2
9
.
Popkova, V.Ya., Galakhov, M.V., and Knu-
nyants, I.L., Izv. Akad. Nauk SSSR, Ser. Khim., 1989,
no. 1, pp. 116 122.
N 10.29.
3
,5-Bis(heptafluoropropyl)-4H-1,2,4-triazole
(
XV). Propionylhydrazide, 3.06 g (30 mmol), was
1
1
0. Ikeda, I., Kogame, Y., and Okahara, M., J. Org.
Chem., 1985, vol. 50, no. 19, pp. 3640 3642.
added with stirring at 0 C to a solution of 13 g
30 mmol) of compound I and 6.06 g (60 mmol) of
(
1. Miki, H. and Gogo, T., JPN Patent Appl. no. 63-
triethylamine in 40 ml of acetonitrile. The mixture
was stirred for 1 h at 0 C and for 3 h at 50 C, cooled,
1
62663, 1988; Chem. Abstr., 1989, vol. 110,
no. 7690y.
poured into 100 ml of water, and treated with CH Cl2
2
1
1
2. Ikeda, I., Tsukamoto, T., and Okahara, M., Chem.
Lett., 1980, no. 3, p. 583.
(
(
3 70 ml). The extract was washed with water
2 50 ml) and dried over MgSO . Distillation fol-
4
3. Chi, K.-W., Kim, S.-J., Park, T.-H., Gatilov, Yu.V.,
Bagryanskaya, I.Yu., and Furin, G.G., J. Fluorine
Chem., 1999, vol. 98, no. 1, pp. 29 36.
lowed by column chromatography on silica gel (eluent
CH Cl ) gave 7.9 g (65%) of compound XV.
2
2
1
4. Chi, K.-W., Furin, G.G., Gatilov, Yu.V., and Bag-
ryanskaya, I.Yu., J. Fluorine Chem., 2000, vol. 103,
no. 2, pp. 105 115.
REFERENCES
1
.
Furin, G.G., Targets in Heterocyclic Systems (Chem-
istry and Properties), Attanasi, O.A. and Spinelli, D.,
Eds., Roma: Ital. Soc. Chem., 1998, vol. 2, pp. 355
15. Petrov, V.A., Belen’kii, G.G., and German, L.S., Izv.
Akad. Nauk SSSR, Ser. Khim., 1985, no. 8, pp. 1934
1935.
4
41.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001