Fluoroalkyl-containing 2-arylhydrazono-1,3-dicarbonyl compounds inthe reactions with ethylenediamine and polyethylenepolyamines

Article abstract of DOI:10.1016/j.jfluchem.2003.11.013

Acyclic N, N′-(poly)ethylene-bis (2-arylazo-1,3-aminovinylketones) are the main products in the reactions of fluoroalkyl-containing 2-arylhydrazono-1,3-diketones with ethylenediamine, diethylenetriamine and triethylenetetramine. Nickel(II) and copper(II)

Full text of DOI:10.1016/j.jfluchem.2003.11.013

Journal of Fluorine Chemistry 125 (2004) 401–407
Fluoroalkyl-containing 2-arylhydrazono-1,3-dicarbonyl compounds in
the reactions with ethylenediamine and polyethylenepolyamines
*
O.G. Khudina, Ya.V. Burgart, V.I. Saloutin , O.N. Chupakhin
Institute of Organic Synthesis, Urals Branch of the Russian Academy of Sciences,
2
0 S. Kovalevskoy Street, GSP-147, 620219 Ekaterinburg, Russia
Received 23 May 2003; received in revised form 6 October 2003; accepted 4 November 2003
Abstract
0
Acyclic N,N -(poly)ethylene-bis(2-arylazo-1,3-aminovinylketones) are the main products in the reactions of fluoroalkyl-containing 2-
arylhydrazono-1,3-diketones with ethylenediamine, diethylenetriamine and triethylenetetramine. Nickel(II) and copper(II) chelates were
0
0
obtained from N,N -ethylene-bis(2-arylazo-1,3-aminovinylketones). 2-Arylhydrazono-3-fluoroacyl esters formed N,N -ethylenediamides of
-arylhydrazono-3-fluoroacylpropionic acids with ethylenediamine. Interaction of 2-arylhydrazono-3-fluoroacyl esters with diethylenetria-
mine and triethylenetetramine resulted in and decomposition products.
2003 Elsevier B.V. All rights reserved.
2
#
Keywords: 2-Arylhydrazono-1,3-diketone; 2-Arylhydrazono-3-oxo ester; Ethylenediamine; Diethylenetriamine; Triethylenetetramine
1
. Introduction
compounds such as pyrazoles and isoxazoles [10]. To our
knowledge there are no literature data on interaction of
2-arylhydrazonosubstituted 1,3-diketones and 3-oxo esters
with ethylenediamine and polyethylenepolyamines.
In the present work the reaction of fluoroalkyl-containing
2-arylhydrazonosubstituted 1,3-diketones 1 and 3-oxo esters
2 with ethylenediamine, diethylenetriamine and triethyle-
netetramine has been studied.
The reaction of 1,3-dicarbonyl compounds with ethylene-
diamine can afford various products. 1,3-Diketones, includ-
ing fluoroalkyl-containing, form either derivatives of 1,
0
4
-diazepine [1,2] or N,N -ethylene-bis(1,3-aminovinyl-
ketones) [3] with this diamine, depending on the reaction
conditions. In the presence of nickel(II) ion 1,3-diketones
react with ethylenediamine to yield nickel chelates of
0
N,N -ethylene-bis(1,3-aminovinylketones) [4,5]. Polyden-
0
tate N,N -bis(1,3-aminovinylketones) are the products of
the reactions of 1,3-diketones with polyethylenepolyamines
2. Results and discussion
[
6]. Template nickel ion condensation of trifluoroacetylace-
2.1. Reactions of 2-arylhydrazono-1,3-diketones with
ethylenediamine, diethylenetriamine and
triethylenetetramine
tone or acetylacetone with triethylenetetramine leads to the
formation of (1,4,7,10-tetraazacyclotrideca-10,12-dienato)-
nickel(II) iodide [7]. Fluoroalkyl-containing 3-oxo esters
interact with ethylenediamine to form the substituted 1,4-
diazepin-5-ones [2,8], imidazolidines [8], acyclic amino-
ethylamides of 3-fluoroacylpropionic acids or dialkyl-N,N -
ethylene-bis(3-amino-2-bytenoates) [9] depending on the
reaction conditions.
It has been found that fluoroalkyl-containing 2-arylhydra-
zono-1,3-diketones 1a–c react differently with ethylenedia-
mine depending on the structure of the fluorinated
0
substituent. 2-Arylhydrazono-1,3-diketone 1a with a
difluoromethyl group cyclizes in methanol at room tempera-
ture into dihydro-1,4-diazepine 3. Under similar conditions
1,3-diketones 1b,c containing ‘‘longer’’ fluoroalkyl substi-
Previouslyweobtainedfluoroalkyl-containing2-arylhydra-
zono-1,3-dicarbonyl compounds and studied their reactions
with a-N,N- and N,O-dinucleophiles resulting in heterocyclic
0
tuents afford acyclic N,N -ethylene-bis(2-arylazo-1,3-amino-
vinylketones) 4b,c (Scheme 1).
*
Unlike the fluorinated compounds 1b,c, 2-arylhydrazono-
substituted acetylacetone 1d under similar conditions
Corresponding author. Fax: þ7-3432-745954.
E-mail address: saloutin@ios.uran.ru (V.I. Saloutin).
0022-1139/$ – see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2003.11.013

402
O.G. Khudina et al. / Journal of Fluorine Chemistry 125 (2004) 401–407
N=NC H -Me-4
6
4
HCF2
Me
N
NH
3
NNHC H -X-4
6
4
C H -X-4
6
4
R1
R2
NH C H NH
2 2 4
2
N
N
MeOH,
R2
O
O
(Et O, Tboil
2
)
R1
C H -OMe-4
6
4
N
1
a-d
O
HN
HN
N
H
O
+
O
1
R2
5
Ph
R
N
N
4b-d
2
1
R = X = Me, R = HCF (1a, 3), H(CF ) (1b, 4b);
2
2 4
C H -X-4
2
1
6
4
R = Ph, X = OMe, R = H(CF ) (1c, 4c);
2
2
2
1
R = R = Me, X = OMe (1d, 4d).
Scheme 1.
forms a mixture of products that is difficult to separate.
0
ethylenedi(poly)amine bridge in compounds 4, 6 and 7 was
established by 13C NMR spectroscopy. In the 13C NMR
However using diethyl ether as a solvent enabled N,N -
ethylene-bis(3-arylazo-4-aminopent-3-en-2-one) 4d to be
obtained (Scheme 1).
2
spectra of compounds 4c, 6a a triplet ( JCÀF ¼ 23:3 Hz (4c),
2
JCÀF ¼ 22:0 Hz (6a)) for the carbon atom attached to the
In the reactions of 2-arylhydrazono-1,3-diketones 1 with
ethylenediamine we observed the single case of heterocyclic
product formation (diazepine 3), while non-substituted 1,3-
diketones can form 1,4-diazepines with ethylenediamine
[1,2]. Attempts to obtain 1,4-diazepines from 2-arylhydra-
zonosubstituted 1,3-diketones 1b-d under conditions used to
cyclize 1,3-diketones [1,2] failed.
polyfluoroalkyl substituent is located at ꢀ180 ppm (Table 1),
which is typical for a carbonyl carbon atom rather than a
carbon at the C¼C bond [11]. Thus, the attack of diamine
proceeds on the carbonyl connected with non-fluorinated
substituent. Such a direction for the addition is also typical
for non-substituted fluorinated 1,3-diketones [3].
Experimental data obtained herein allow us to conclude
that fluorinated 2-arylhydrazono-1,3-diketones 1 possess
lower reactivity towards ethylenediamine (polyethylenepoly-
amines) compared with non-substituted analogues. Thus,
2-Arylhydrazono-1,3-diketones 1b,c,e react with diethy-
lenetriamine and triethylenetetramine to give the penta- and
0
hexadentate
6
2
N,N -bis(2-arylazo-1,3-aminovinylketones)
a,b, and 7a,b, respectively (Scheme 2).
-Arylhydrazono-1,3-diketones 1 condense with ethyle-
0
the formation of acyclic N,N -ethylene-bis(1,3-aminovi-
nylketones) from fluoroalkyl-containing 1,3-diketones is
an exothermal process carried out at lower temperatures
[3], while 2-arylhydrazono-1,3-diketones 1 react with ethy-
lenediamine (polyethylenepolyamines) at room temperature
with incomplete conversion of starting compounds. How-
ever, by-products were formed already under these condi-
tions, which was determined by thin-layer chromatography.
nediamine (polyethylene-polyamines) in a ratio of 2:1 at one
carbonyl group to give products 4, 6 and 7. In the case of the
asymmetric fluoroalkyl-containing 2-arylhydrazono-1,3-
diketones 1 the reaction may proceed either on the carbonyl
connected with the non-fluorinated substituent or the car-
0
bonyl of the fluorinated moiety. The position of N,N -(poly)-
C H -X-4
6
4
N
N
R2
R1
NNHC H -X-4
6
4
C H -OMe-4
O
N
6
4
1
R2
R
H
H
N
NH C H (NHC H ) NH
N
H
O
2
2
4
2
4
n
2
HN
N
+
O
O
MeOH
(
Et O)
n
2
1
b,c,e
O
5
Ph
1
R2
R
N
N
1
2
R = H(CF ) , R = X = Me (1b), n = 1 (6a), 2 (7a);
2
4
2
C H -X-4
6
4
1
R = CF , R = Ph, X = Me, n = 1 (1e, 6b);
3
1
2
6a,b, 7a,b
R = H(CF ) , R = Ph, X = OMe (1c), n = 2 (7b)
2
2
Scheme 2.

O.G. Khudina et al. / Journal of Fluorine Chemistry 125 (2004) 401–407
403
Table 1
13CNMR spectral data for compounds 4c, 7a (dC, ppm; J(13C–19F), Hz) in CDCl
3
1
C
2–5
C
6
7
8
C
9
C
10
C
11
12
13
C
14
C
15–16
Compounds
C
C
C
C
C
4
7
7
c
55.58 114.74–160.00
163.85
142.62 180.36 T(23.3) 107.76–115.03 46.29
a, I
a, II
16.84 120.84–138.25 21.19 163.97 149.38 179.44 T(22.0) 105.46–113.20
16.99 121.09–138.26 21.26 164.06 149.38 179.65 T(22.0) 105.46–113.20
43.77–52.74
41.34–56.04
C H -X-4
N
C H -X-4
6
4
6
4
position 2, the complexation does not occur due to steric
factors. We have found that nickel complexes 8b,c can be
obtained by a one-step template method from ethylenedia-
mine and 2-arylhydrazono-1,3-diketones 1b,d in the presence
of nickel(II) acetate (Scheme 3).
N
N
N
NNHC H -X-4
6 4
Me
Me
R
R
R
R
Me
O
N
N
Met(OAc)
2
O
N
Met
N
H
H
O
O
1
b,d
O
O
0
+
AttemptstoobtainN,N -ethylene-bis(2-arylazo-1,3-amino-
Me
Me
R
Met(OAc)
2
vinylketone) 4a with difluoromethyl substituents using a
template method failed due to many by-products being
formed.
N
N
+
N
N
NH C H NH
2
2
4
2
C H -X-4
C H -X-4
6 4
6
4
4
b,d
8a-c
R = H(CF ) , X = Me (1b, 4b), Met = Cu (8a), Ni (8b);
R = Me, X = OMe (1d, 4d), Met = Ni (8c).
2
4
2.2. Reactions of 2-arylhydrazono-3-fluoroacyl esters with
ethylenediamine, diethylenetriamine and
triethylenetetramine
Scheme 3.
One such by-process is the acid decomposition of 2-aryl-
hydrazono-1,3-diketones 1 resulting in product 5, isolated
from the reaction of 1,3-diketone 1c.
3-Oxo esters, including fluoroalkyl-substituted, can react
with ethylenediamine at the keto group, ester fragment
[9,14] or at both these centers [2,8,14]. We have found that
2-arylhydrazono-3-fluoroacyl esters 2a,b condense with
ethylenediamine at the ester group to give N,N -ethylene-
diamides 9a,b (Scheme 4).
Compared with 2-arylhydrazono-1,3-diketones 1, fluoro-
alkyl-containing 2-arylhydrazono-3-oxo esters 2 in reac-
tions with ethylenediamine have a greater tendency to
undergo various side processes. The acid cleavage product
10 was isolated from the reaction of 2-arylhydrazono-3-oxo
ester 2b with ethylenediamine under mild conditions.
Attempts to obtain cyclic products from these reactions
were unsuccessful.
0
It has been shown that N,N -ethylene-bis(2-arylazo-1,3-
0
aminovinylketone) 4 possesses a complexation ability like
the non-substituted compounds of this class [3]. The treat-
ment of compounds 4b,d with nickel(II) or copper(II) acetate
gives the corresponding metal chelates 8a–c (Scheme 3).
The template method is widely used for synthesis of similar
nickel complexes [4,12,13]. However, it has been noted [12],
that tri- and hexa-fluoroacetylacetones undergo Ni(II) tem-
plate reactions with ethylenediamine to form nickel bis(1,3-
diketonates) only. It has been also claimed [12] that in the
case of 1,3-diketones having substituents (phenyl, methyl) in
H
N
N
O
R
O
R
H
N
4
-Me-C H
N
O
N
HH
N C H -Me-4
6
4
6
4
NNHC H -Me-4
6
4
Rf
O
OMe
f
f
9a,b
NH C H NH
2
+
2
2
4
O
O
N
H
2
a,b
MeO
N C H -Me-4
6
4
O
Rf = H(CF ) (2a, 9a); C F (2b, 9b).
10
2
2
4
9
Scheme 4.
NNHC H -Me- 4
H
O
Me
6
4
4
-Me-C H
N
N
N
O
N
N
C H -Me-4
Me
OEt
6
4
6
4
HH
N
NH C H NH
2
2
4
2
O
O
O
MeOH,
Me
OEt
1
1
2
c
o
2
0 C
Scheme 5.

404
O.G. Khudina et al. / Journal of Fluorine Chemistry 125 (2004) 401–407
H(CF2)2
O
NNHC H -Me-4
HN
HN
H N
H(CF2)2
C H -Me- 4
N
6
4
6
4
H
O
H(CF2)
2
OMe
N
NH C H (NHC H ) NH
2
2
4
2
4
n
2
+
n
O
O
MeOH (Et O)
2
2
a
OMe
O
1
0
1
2a,b
n = 1 (a), 2 (b).
Scheme 6.
In contrast to 2-arylhydrazono-3-fluoroacyl esters 2a,b,
by the atomic absorption method on a Perkin Elmer PE 403
spectrophotometer. Column chromatography was performed
on silica gel L 100/250.
under similar conditions 2-arylhydrazonosubstituted ethyl
acetylacetate 2c forms compound 11 as a result of addition
of ethylenediamine on ester fragment of one 3-oxo ester and
on ketogroup of other 3-oxo ester (Scheme 5).
4.1. Synthesis of compounds 3, 4b-d, 5
Evidently 2-arylhydrazono-3-fluoroacyl esters 1a,b react
with ethylenediamine at the ester group to give symmetrical
amides 9a,b due to the presence of the electron-withdrawing
fluoroalkyl substituents.
Ethylenediamine (1 mmol) was added to a solution of 2-
arylhydrazono-1,3-diketone 1a–d (1 mmol) in methanol
(8 ml) (diethyl ether for 4d). The reaction mixture was kept
for 24 h at room temperature (30 h at boiling temperature for
4d). The precipitate formed was filtered off, recrystallized
from a mixture of benzene: hexane (1:10) to give compounds
3, 4b–d as yellow powders, are 5 as a white powder.
Acid decomposition is the basic process in the reactions of
-arylhydrazono-3-fluoroacyl ester 2a with diethylenetria-
2
mine and triethylenetetramine (Scheme 6) as shown by
isolation of products 12a,b and 10b.
4.1.1. 5-Difluoromethyl-6-(p-methylphenyl)azo-7-methyl-
2,3-dihydro- H-1,4-diazepine (3)
1
3
. Conclusion
1
Yield, 60%; mp, 172–173 8C. H NMR (CDCl ): d 2.38
3
Introduction of the arylhydrazono-substituent in position
of fluoroalkyl-containing 1,3-dicarbonyl compounds
affects their reactivity towards, ethylenediamine. In contrast
to non-substituted analogues these compounds are conver-
ted to heterocycles with difficulty. 2-Arylhydrazono-1,
(3H, s, CH ), 2.54 (3H, s, CH ), 3.67 (2H, m, CH ), 4.11
1
3
3
2
2
(2H, m, CH ), 5.22 ( H, br. s, NH), 6.68 (1H, t, HCF ,
2 2
2
JHÀF ¼ 56:0 Hz), 7.36 (4H, m, C H ) ppm. 19F NMR
6
4
2
(CDCl ): d 41.74 (4F, d, 2 HCF , J
HÀF
¼ 56:0 Hz) ppm.
3
2
IR: 3430, 1590 (NH), 1625, 1555, 1535 (C¼N, C¼C, N¼N)
À1
þ
3
-dicarbonyl compounds react with ethylenediamine and
polyethylenediamine at the carbonyl associated with the non-
cm . MS, m/z (I (%)): 279 (10.06) [M þ 1] , 278 (57.52)
rel
þ
[M] , 131 (16.42), 130 (26.52), 120 (26.34) [HN¼N–C H –
6
4
0
þ
þ
fluorinated substituent to form acyclic products. The N,N -
ethylene-bis(2-arylazo-1,3-aminovinylketones) obtained are
of interest due to their complexation ability.
CH ] , 119 (31.09) [N¼N–C H –CH ] , 107 (19.91) [M–
þ
6 4 3 2 6 4
3
6
4
3
NH¼N–C H –CH , CF H] , 104 (14.42), 91 (100) [C H –
þ
3 14 16 2 4
CH ] , 65 (13.74). Analysis: Calc. for C H F N : C, 60.4;
H, 5.8; F, 13.65; N, 20.1%. Found: C, 60.4; H, 5.9; F, 14.0; N,
20.0%.
4
. Experimental
0
4.1.2. N,N -Ethylene-bis(6-(p-methylphenyl)azo-7-amino-
1,1,2,2,3,3,4,4-octafluoro-6-octen-5-one) (4b)
Melting points were measured in open capillaries and are
uncorrected. Infrared spectra were recorded on a Specord 75
IR spectrophotometer at 4000–400 cm in vaseline oil
(compounds 4b,c, 5, 8b,c, 9a–e, 10) and in 0.01 M CHCl
solution (3, 4b,d, 8a, 11). H and C NMR spectra were
1
Yield, 53%; mp, 134–135 8C. H NMR (CDCl ): d 2.29
3
À1
(6H, s, 2 CH ), 2.59 (6H, s, 2 CH ), 3.92 (4H, s, 2 CH ), 6.20
2
3
3
2
3
(2H, tt, 2 H(CF ) , J
2 4
HÀF
¼ 52:0, J
HÀF
¼ 5:7 Hz), 7.02
3
1
13
19
(8H, m, 2 C H ), 15.78 (2H, br. s, 2 NH) ppm. F NMR
6 4
(CDCl ): d 24.58 (4F, dt, 2 HCF , 2J
1
measured on a Bruker DRX-400 spectrometer ( H, 400 MHz,
13C, 100.6 MHz) relative to SiMe4. 19
¼ 52:0,
3
2
FÀH
3
F NMR spectra were
obtained on a Tesla BS-587 A spectrometer ( F, 75 MHz)
using C F as an internal standard. Mass spectra were mea-
J
FÀF
¼ 7:9 Hz), 32.49 (4F, m, 2CF ), 39.82 (4F, m, 2
2
1
9
CF ), 51.66 (4F, m, 2 CF ) ppm. IR: 3430, 1585 (NH),
2
2
À1
1655 (C¼O), 1600, 1585 (N¼N, C¼C) cm . UV (chloro-
6
6
sured on a Varian MAT-311A spectrometer. UV spectra were
recorded on a Shimadzu UV-2401 PC spectrophotometer.
Microanalyses were carried out on a Carlo Erba CHNS-O EA
form), l (E): 218 (10 500), 244 (15 860), 374 (40 140)
MAKC
nm. Analysis: Calc. for C H F N O : C, 46.16; H, 3.39;
F, 36.51; N, 10.09%. Found: C, 46.07; H, 3.44; F, 36.62; N,
10.14%.
3
2 28 16 6 2
1
108 elemental analyzer. Copper and nickel were determined

O.G. Khudina et al. / Journal of Fluorine Chemistry 125 (2004) 401–407
405
0
0
4.1.3. N,N -Ethylene-bis(4-(p-methoxyphenyl)azo-5-
amino-1,1,2,2-tetrafluoro-5-phenyl-4-penten-3-one) (4c)
4.2.2. Amino-N,N -diethylene-bis(3-(p-methylphenyl)azo-
4-amino-1,1,1-trifluoro-4-phenyl-3-butene-2-one) (6b)
Yield after reprecipitation from chloroform/ethanol, 55%;
1
Yield after reprecipitation from acetone/methanol, 42%;
1
mp, 205–206 8C. H NMR (CDCl ): d 3.42 (4H, m, 2 CH ),
3
3
mp, 154-156 8C. H NMR (CDCl ): d 2.37 (6H, s, 2 CH ),
3
2
3
3
2
3
.84 (6H, s, 2 OCH ), 6.30 (2H, tt, 2 H(CF ) , JHÀF ¼ 53:8,
2.84 (4H, t, 2 CH , JHÀH ¼ 5:8 Hz), 3.29 (4H, m, 2 CH ),
3
2 2
2
2
JHÀF ¼ 5:6 Hz), 6.87–7.46 (18H, m, 2 C H , 2 C H ),
7.17–7.19 (8H, m, 2 C H ), 7.47–7.48 (10H, m, 2 C H ),
6 4 6 5
14.91 (2H, br. s, 2 NH) ppm. 19F NMR (CDCl ): d 92.01
6
4
6
5
19
1
(
2
(
5
3
5.03 (2H, br. s, 2 NH) ppm. F NMR (CDCl ): d 25.20
3
3
2
3
4F, dt, HCF , J
¼ 53:8, J
¼ 7:9 Hz), 41.71 (4F, m,
(CF , s) ppm. IR: 3305, 3270, 2710, 1570, 1590 (NH),
À1
2
FÀH
FÀF
3
CF ) ppm. IR: 3310, 1590 (NH), 1655 (C¼O), 1550, 1500
1675 (C¼O), 1650, 1550, 1530 (C¼C, N¼N) cm
.
2
À1
N¼N, C¼C) cm . Analysis: Calc. for C H F N O : C,
Analysis: Calc. for C H F N O : C, 62.04; H, 4.80; F,
38 35 6 7 2
3
8
32
8
6
4
7.87; H, 4.09; F, 19.27; N, 10.66%. Found: C, 57.77; H,
.94; F, 19.23; N, 10.73%.
15.49; N, 13.33%. Found: C, 62.03; H, 4.85; F, 15.67; N,
13.55%.
0
4
4
.1.4. N,N -Ethylene-bis(3-(p-methoxyphenyl)azo-
-amino-3-penten-2-one) (4d)
4.3. Synthesis of compounds 7a,b
Yield after recrystallization from acetone, 25%; mp, 184–
1
Triethylenetetramine (1 mmol) was added to a solution of
2-arylhydrazono-1,3-diketone 1b,c (1 mmol) in diethyl
ether (8 ml) (methanol for 7b). The reaction mixture was
refluxed for 24 h. The resulting precipitate was filtered off,
recrystallized from ethanol to give compounds 7a,b as
yellow powders.
1
s, 2 CH ), 3.78 (6H, s, 2 OCH ), 3.84 (4H, s, 2 CH ), 6.91
(
85 8C. H NMR (CDCl ): d 2.49 (6H, s, 2 CH ), 2.55 (6H,
3
3
3
3
2
8H, s, 2 C H ) ppm. IR: 3430, 1590 (NH), 1635 (C¼O),
6
4
À1
1570, 1490 (N¼N, C¼C) cm . Analysis: Calc. for
C H N O : C, 63.40; H, 6.55; N, 17.06%. Found: C,
26 32 6 4
6
3.05; H, 6.77; N, 16.75%.
0
4.3.1. Ethylenediamino-N,N -diethylene-
bis(6-(p-methylphenyl)azo-7-amino-1,1,2,2,3,3,4,4-
4.1.5. 2-(p-Methoxyphenyl)hydrazono-1-phenyl-1-
ethanone (5)
octa-fluoro-6-octen-5-one) (7a)
Yield, 40%; mp, 153–155 8C. H NMR (CDCl , a mix of
1
Yield after column chromatography (with CHCl as an
3
3
1
eluent), 35%; mp, 107–108 8C. H NMR (CDCl ): d 3.82
tautomers (I):(II) ꢀ3:2) I: d 2.33 (6H, s, 2 CH ), 2.46 (6H, s,
3
3
1
(
3H, s, OCH ), 6.91–7.99 (9H, m, C H , C H ), 7.68 ( H, s,
2 CH ), 2.85 (4H, s, 2 CH ), 2.89 (4H, t, 2 CH ,
2
3
6
4
6
5
3
2
3
CH¼), 14.67 (1H, ws, NH) ppm. IR: 3050, 1555 (NH), 1610
JHÀH ¼ 5:8 Hz), 3.36 (4H, m, 2 CH ), 6.24 (2H, tt, 2
2
À1
2
3
(
Calc. for C H N O : C, 70.85; H, 5.55; N, 11.02%. Found:
C¼O), 1590, 1520, 1500 (C¼N, C¼C) cm . Analysis:
H(CF ) , JHÀF ¼ 52:2, JHÀF ¼ 5:7 Hz), 7.16–7.52 (8H,
2
4
m, 2 C H ); II: d 2.38 (6H, s, 2 CH ), 2.60 (6H, s, 2
1
5
14
2
2
6 4 3
C, 70.46; H, 5.35; N, 10.72%.
CH ), 2.63 (4H, br. s, 2 CH ), 2.71 (4H, t, 2 CH ,
3
3 2 2
JHÀH ¼ 5:8 Hz), 3.60 (4H, m, 2 CH ), 6.25 (2H, tt, 2
2
2
3
4
.2. Synthesis of compounds 6a,b
H(CF ) , JHÀF ¼ 52:2, JHÀF ¼ 5:7 Hz), 7.20–7.59 (8H,
19
6 4 3
2
4
m, 2 C H ) ppm. F NMR (CDCl , (I):(II) ꢀ 3:2) I: d
Diethylenetriamine (1 mmol) was added to a solution of
-arylhydrazono-1,3-diketone 1b,e (1 mmol) in methanol
8 ml). The reaction mixture was kept for 24 h at room
24.32 (4F, m, 2 HCF ), 32.23 (4F, m, 2 CF ), 39.58 (4F, m, 2
2 2
2
(
CF ), 52.05 (4F, m, 2 CF ); II: d 24.57 (4F, m, 2 HCF ),
2
2
2
32.39 (4F, m, 2 CF ), 39.47 (4F, m, 2 CF ), 50.24 (4F, m, 2
CF ) ppm. IR: 3290, 2775, 1600 (NH), 1645, 1635 (C¼O),
2 2
temperature (30 h at boiling temperature for 6b). The
formed precipitate was filtered off, recrystallized from
CH Cl to give compounds 6a,b as yellow powders.
2
À1
1570, 1545 (C¼C, N¼N) cm . Analysis: Calc. for
C H F N O : C, 47.06; H, 4.17; F, 33.09; N, 12.20%.
36 38 16 8 2
2
2
Found: C, 47.69; H, 4.03; F, 33.30; N, 12.27%.
0
4
.2.1. Amino-N,N -diethylene-bis(6-(p-methylphenyl)azo-
-amino-1,1,2,2,3,3,4,4-octafluoro-6-octen-5-one) (6a)
0
7
4.3.2. Ethylenediamino-N,N -diethylene-
bis(4-(p-methoxyphenyl)azo-5-amino-1,1,2,2-tetra-
1
Yield, 44%; mp, 163–164 8C. H NMR (CDCl ): d 2.35
3
(
6H, s, 2 CH ), 2.48 (6H, s, 2 CH ), 3.10 (4H, t, 2 CH ,
J
fluoro-5-phenyl-4-penten-3-one) (7b)
Yield after reprecipitation from chloroform/ethanol,
3
3
2
3
¼ 5:8 Hz), 3.62 (4H, m, 2 CH ), 6.22 (2H, tt, 2
HÀH
2
2
3
1
H(CF ) , JHÀF ¼ 52:2, JHÀF ¼ 5:7 Hz), 7.14–7.41 (8H,
42%; mp, 232–234 8C. H NMR (CDCl ): d 2.53 (4H,
2
4
3
1
9
3
m, 2 C H ), 15.06 (2H, br. s, 2 NH) ppm. F NMR
6
m, 2 CH , J
¼ 5:4 Hz), 3.25 (4H, m, 2 CH ), 3.77
4
2
HÀH
(4H, s, 2 CH ), 3.86 (6H, s, 2 OMe), 6.43 (2H, tt, 2 H(CF ) ,
2
2
(
3
CDCl ): d 24.48 (4F, dt, 2 HCF , JFÀH ¼ 52:2,
3
2
2
2 2
JFÀF ¼ 8:6 Hz), 32.33 (4F, m, 2 CF ), 39.69 (4F, m, 2
2J
¼ 54:3, 3J
¼ 5:7 Hz), 6.86–7.63 (18H, m, 2
2
HÀF
HÀF
CF ), 52.03 (4F, m, 2 CF ) ppm. IR: 3440, 3385, 3280,
2
C H , 2 C H ), 14.21 (2H, ws, 2 NH) ppm. IR: 2700,
6 4 6 5
2
À1
1
Analysis: Calc. for C H F N O : C, 46.64; H, 3.80; F,
3
1
550 (NH), 1645 (C¼O), 1580, 1570 (C¼C, N¼N) cm
.
2660, 1570, (NH), 1655 (C¼O), 1590, 1525, 1490
À1
(C¼C, N¼N) cm . Analysis: Calc. for C H F N O :
42 42 8 8 2
3
4
33 16
7
2
4.71; N, 11.20%. Found: C, 46.57; H, 3.93; F, 34.80; N,
0.92%.
C, 57.66; H, 4.84; F, 17.37; N, 12.81%. Found: C, 57.52; H,
4.73; F, 17.59; N, 12.41%.

406
O.G. Khudina et al. / Journal of Fluorine Chemistry 125 (2004) 401–407
4
.4. Synthesis of metal chelates 8a–c
a) A solution of copper(II) acetate monohydrate (nickel
acetate tetrahydrate for 8b,c) (1 mmol) in ethanol (5 ml)
4.5. Synthesis of compounds 9a,b, 10, 11
(
Ethylenediamine (1 mmol) was added to a solution of 2-
arylhydrazono-3-oxo esters 2a–c (1 mmol) in methanol
(8 ml). The reaction mixture was kept for 48 h at room
temperature. The resulting solid was filtered off, reprecipi-
tated from acetone/methanol to give compounds 9a,b, 11 as
yellow powders, 10 as a white powder.
0
was added to a solution of N,N -ethylene-bis(2-arylazo-
1
The reaction mixture was refluxed for 10 min. The pre-
cipitation with water gave chelates 8a–c as deep-brown
powders.
,3-aminovinylketone) 4b,d (1 mmol) in ethanol (5 ml).
0
(b) A mixture of nickel(II) acetate tetrahydrate (1 mmol),
-arylhydrazono-1,3-diketone 1b,d (2 mmol) and ethylene-
4.5.1. N,N -Ethylene-bis(2-(p-methylphenyl)hydrazono-3-
oxo-4,4,5,5-tetrafluoropentanamide) (9a)
2
diamine (1 mmol) in ethanol (10 ml) was refluxed for 3 h.
1
Yield, 48%; mp, 190–191 8C. H NMR (CDCl ): d 2.38
3
The solvent was removed under reduced pressure. Column
chromatography (with CHCl as an eluent) gave compounds
(6H, s, 2 CH ), 3.61 (4H, m, 2 CH ), 6.35 (2H, tt, 2 H(CF ) ,
3
2
2 2
2
3
JHÀF ¼ 53:4, JHÀF ¼ 5:5 Hz), 7.27 (8H, m, 2 C H ), 9.02,
19
3
3
6 4
8
b,c.
15.27 (4H, 2 br. s, 4 NH) ppm. F NMR (CDCl ): d 25.59
2
3
(
4F, dt, 2 HCF , JFÀH ¼ 53:4, JFÀF ¼ 7:9 Hz), 42.72 (4F,
2
0
4
1
.4.1. N,N -Ethylene-bis(6-(p-methylphenyl)azo-7-amino-
,1,2,2,3,3,4,4-octafluoro-6-octen-5-onato)copper(II) (8a)
Yield after reprecipitation from chloroform/hexane, 96%;
m, 2 CF ) ppm. IR: 3320, 1580 (NH), 1660, 1650 (C¼O),
2
À1
1620, 1550, 1505 (C¼N, C¼C) cm . Analysis: Calc. for
C H F N O : C, 49.06; H, 3.80; F, 23.88; N, 13.20%.
2
6 24 8 6 4
mp, 164–165 8C. IR: 1640 (C¼O), 1570, 1535, 1490 (N¼N,
Found: C, 48.95; H, 4.05; F, 23.80; N, 13.19%.
À1
C¼C) cm . UV (chloroform), l
(E): 220 (12 200), 243
19 120), 346 (33 920), 392 (31 180), 516 sh (1280) nm.
MAKC
0
(
Analysis: Calc. for C H F N O Cu: C, 42.99; H, 2.93; F,
4.5.2. N,N -Ethylene-bis(2-(p-methylphenyl)hydrazono-3-
oxo-4,4,5,5,6,6,7,7-nonafluoroheptan-amide) (9b)
3
2 26 16 6 2
3
3
4.00; N, 9.40; Cu, 7.11%. Found: C, 43.03; H, 2.88; F,
4.18; N, 9.43; Cu, 7.06%.
Yield after recrystallization from ethanol, 38%; mp, 76–
1
78 8C. H NMR (CDCl ): d 2.37 (6H, s, 2 CH ), 3.62 (4H, m,
3
3
2
CH ), 7.28 (8H, m, 2 C H ), 9.03, 15.39 (4H, 2 br. s, 4 NH)
2 6 4
19
0
4
1
.4.2. N,N -Ethylene-bis(6-(p-methylphenyl)azo-7-amino-
,1,2,2,3,3,4,4-octafluoro-6-octen-5-onato)nickel(II) (8b)
ppm. F NMR (CDCl ): d 36.59 (4F, m, CF ), 41.14 (4F, m,
3
2
2 CF ), 51.21 (4F, m, 2 CF ), 80.93 (6F, m, 2 CF ) ppm. IR:
3330, 1575 (NH), 1665, 1650 (C¼O), 1515, 1500 (C¼N,
2 2 3
Yield after column chromatography (with benzene as an
1
À1
eluent), 85% (a) and 65% (b); mp, 190–191 8C. H NMR
C¼C) cm . Analysis: Calc. for C H F N O : C, 41.30;
3
0 22 18 6 4
(
CDCl ): d 2.24 (6H, s, 2 CH ), 2.57 (6H, s, 2 CH ), 3.47
H, 2.54; F, 39.19; N, 9.63%. Found: C, 41.02; H, 2.50; F,
39.00; N, 9.48%.
3
3
3
2
(
3
4H, br. s, 2 CH ), 6.22 (2H, tt, 2 H(CF ) , JHÀF ¼ 52:1,
19
6 4
2
2 4
JHÀF ¼ 5:6 Hz), 6.98 (8H, m, 2 C H ) ppm. F NMR
2
(
3
CDCl ):
3
d
24.45 (4F, dt, 2 HCF , JFÀI ¼ 52:1,
4.5.3. Methyl-2-(p-methylphenyl)hydrazonoethanoate (10)
Yield after recrystallization from mixture of benzene:
hexane (1:1), 54%; mp, 177–178 8C. H NMR (DMSO-
2
J
¼ 7:9 Hz), 32.40 (4F, m, 2 CF ), 39.60 (4F, m, 2
FÀF
2
1
CF ), 51.09 (4F, m, 2 CF ) ppm. IR: 1640 (C¼O), 1570,
2
2
À1
1
2
535, 1490 (N¼N, C¼C) cm . UV (methanol), l
(E):
03 (36 500), 242 (30 620), 290 (28 460), 360 (42 200), 477
d /CCl ): d 2.26 (3H, s, CH ), 3.72 (3H, s, OCH ), 7.01 (4H,
MAKC
6
4
3
3
1
m, C H ), 7.10 (1H, m, CH¼), 11.02 ( H, br. s, NH) ppm.
6
4
sh (7700) nm. Analysis: Calc. for C H F N O Ni: C,
3
IR: 3240 (NH), 1690 (C¼O), 1530, 1500 (C¼N, C¼C)
2 26 16 6 2
À1
4
4
3.22; H, 2.95; F, 34.18; N, 9.45; Ni, 6.60%. Found: C,
3.50; H, 2.89; F, 33.84; N, 9.42; Ni, 6.54%.
cm . Analysis: Calc. for C H N O : C, 62.49; H, 6.29; N,
1
0 12 2 2
14.57%. Found: C, 62.47; H, 6.23; N, 14.81%.
0
0
4
3
.4.3. N,N -Ethylene-bis(3-(p-methylphenyl)azo-4-amino-
-penten-2-onato)nickel(II) (8c)
4.5.4. N,N -Ethylene-(2-(p-methylphenyl)hydrazono-3-
0
0
oxobutanamide)(ethyl-2 -(p-methylphenyl)-azo-3 -amino-
0
Yield after reprecipitation from chloroform/hexane, 95%
1
2 -butenoate) (11)
Yield after recrystallization from acetone, 43%; mp, 139–
(
(
3
(
(
5
(
2
(
a) and 57% (b); mp, 204–2058C. H NMR (CDCl ): d 2.41
3
1
6H, s, 2 CH ), 2.53 (6H, s, 2 CH ), 3.75 (6H, s, 2 OCH ),
.39 (4H, br. s, 2 CH ), 6.87 (8H, m, 2 C H ) ppm. IR: 1630
140 8C. H NMR (CDCl ): d 1.38 (3H, t, OCH CH ,
3
3
3
3
2
3
3
JHÀH ¼ 7:1 Hz), 2.31 (3H, s, CH ), 2.34 (3H, s, CH ),
2
6
4
À1
3
3
C¼O), 1590, 1525, 1490 (N¼N, C¼C) cm . MS, m/z (Irel
2.36 (3H, s, CH ), 2.44 (3H, s, CH ), 3.68 (2H, m, CH ), 3.76
3 3 2
þ
þ
3
%)): 551 (14.64) [M þ 1] , 550 (44.64) [M] , 549 (33.33),
48 (100.00), 229 (14.98), 228 (90.73), 182 (12.14), 179
10.91), 95 (21.68), 68 (12.14). UV (methanol), lMAKC (E):
03 (39 500), 226 (32 400), 290 (27 600), 354 (39 600), 484
11 000) nm. Analysis: Calc. for C H N O Ni: C, 56.86;
(2H, m, 2 CH ), 4.30 (2H, q, OCH CH , JHÀH ¼ 7:1 Hz),
2
2
3
7.09–7.34 (8H, m, 2 C H ), 9.65, 14.60, 15.19 (3H, 3 br. s, 3
6 4
NH) ppm. IR: 3450, 3250 (NH), 1680, 1640 (C¼O), 1575,
À1
1500 (C¼N, C¼C) cm . MS, m/z (I (%)): 493 (20.24)
rel
þ
þ
[M þ 1] , 492 (67.23) [M] , 246 (13.93) [CH –C(¼O)–
2
6
30
6
4
3
þ
H, 5.51; N, 15.30; Ni, 10.69%. Found: C, 56.55; H, 5.40; N,
5.40; Ni, 10.74%.
C( ¼ N – NH – C H – CH ) –C( ¼ O)–NH–CH –CH ] or
6
4
3
2
2
þ
1
[ C H O – C( ¼ O)–C(¼N–NH–C H –CH )–C(CH )¼N] ,
2
5
6
4
3
3

O.G. Khudina et al. / Journal of Fluorine Chemistry 125 (2004) 401–407
407
1
55 (13.78) [CH –C(¼O)–C(¼N–NH )–C(¼O)–NH–CH¼
References
3
2
þ
þ
2
CH ] or [C H O–C(¼O)–CH¼C(CH )–NH–CH¼CH ] ,
2
2
5
3
þ
1
32 (12.44) [CH ¼ N – N¼ C H ¼ CH ] , 119 (41.51)
[1] G. Schwarzenbach, K. Lutz, Helv. Chim. Acta 23 (1940) 1139;
D. Lloyd, D.R. Marshall, J. Chem. Soc. (1956) 2597.
2
6
4
2
þ
[N ¼ N – C H – CH ] , 109 (13.05), 107 (75.23) [ H N–
C H –CH ] , 106 (100) [NH–C H –CH ] , 97 (12.02)
6
4
3
2
þ
þ
[2] Z.E. Skryabina, Ya.V. Burgart, V.I. Saloutin, Izv. Akad. Nauk SSSR
Ser. Khim. (Russ. Chem. Bull) (1991) 890.
6
4
3
6
4
3
þ
[
HC(¼N)–C(¼O)–NH–CH¼CH ] or [CH ¼N–CH¼CH–
2
2
[
3] P.J. McCarthy, R.J. Hovey, K. Veno, A.F. Martell, J. Am. Chem. Soc.
77 (1955) 5820;
þ
þ
3
NH–C(¼O)] , 91 (83.88) [C H –CH ] , 79 (12.26). Analy-
6
4
sis: Calc. for C H N O : C, 63.40; H, 6.55; N, 17.06%.
2
M.J. Crookes, P. Roy, D.L. Williams, J. Chem. Soc. Perkin Trans. II
6 32 6 4
(
1989) 1015;
Found: C, 63.71; H, 6.60; N, 17.17%.
S.E. Livingstone, J.H. Mayfield, Austr. J. Chem. 28 (1975) 1547.
4] L.J. Boucher, E.J. Olszewski, R.W. Oehmke, J.C. Bailar, D.F. Martin,
Inorg. Chem. 2 (1963) 661.
[
[
[
4.6. Reactions of 2-arylhydrazono-3-oxo ester 2a with
diethylenetriamine or triethylenetetramine
5] R.H. Holm, G.W. Everett, A. Chakravorty, Prog. Inorg. Chem. 7
(
1966) 183.
6] S.C. Cummings, R.E. Sievers, Inorg. Chem. 11 (1972) 1483;
W.N. Wallis, S.C. Cummings, Inorg. Chem. 13 (1974) 988.
7] S.C. Cummings, R.E. Sievers, Inorg. Chem. 9 (1970) 1131.
8] M.M. Joulle, M.J. Slusarczuk, A.S. Dey, P.V. Venuto, R.H. Yocum, J.
Org. Chem. 32 (1967) 4103.
A mixture of 2-arylhydrazono-3-oxo ester 2a (1 mmol)
and diethylenetriamine or triethylenetetramine (1 mmol)
was stirred in 8 ml of methanol (diethyl ether) for 48 h.
The solvent was removed. Column chromatography (with
chloroform:methanol (1:10) as an eluent) gave products 10
[
[
[9] V.I. Saloutin, A.N. Fomin, K.I. Pashkevich, Izv. Akad. Nauk SSSR,
Ser. Khim. (Russ. Chem. Bull.) (1985) 144.
(
0.14 g, 66%) and 12a (0.10 g, 63%; mp, 138–139 8C; [15])
or compounds 10 (0.12 g, 58%) and 12b (0.09 g, 52%; mp,
16–117 8C; [15]) as white precipitates.
[
[
10] Ya.V. Burgart, A.S. Fokin, O.G. Kuzueva, O.N. Chupakhin, V.I.
Saloutin, J. Fluorine Chem. 92 (1998) 101.
1
11] B.I. Ionin, B.A. Ershov, A.I. Kol’tsov, YaMR-Spektroskopiya v
organicheskoi khimii, NMR Spectroscopy in Organic Chemistry,
Khimiya, Leningrad, 1983, p. 17 (in Russian).
[
12] D.F. Martin, E.J. Olzewski, J. Inorg. Nucl. Chem. 28 (1966)
Acknowledgements
1
073.
[
[
[
13] D.F. Martin, E.J. Olzewski, J. Inorg. Nucl. Chem. 26 (1964) 1577.
14] C.M. Hofmann, S.R. Safir, J. Org. Chem. 27 (1962) 3565.
15] V.I. Saloutin, Z.E. Skryabina, Ya.V. Burgart, S.V. Kiseleva, Izv.
Akad. Nauk, Ser. Khim. (Russ. Chem. Bull.) (1992) 2591.
The authors wish to thank Russian Foundation for Basic
Research (grant no. 03-03-33118 and no. 03-03-06471) and
INTAS (grant no. 00-711) for financial support of this work.