Reactions of α,β-Dibromo-β-nitrostyrenes with Acetylacetone and Ethyl Acetoacetate

Article abstract of DOI:10.1023/A:1025652922798

The reactions of α,β-dibromo-β-nitrostyrenes with acetylacetone and ethyl acetoacetate were studied. The structures of the products were determined by 1H NMR, IR, and UV spectroscopy. The products derived from acetylacetone were converted into copper chel

Full text of DOI:10.1023/A:1025652922798

Russian Journal of General Chemistry, Vol. 73, No. 4, 2003, pp. 603 606. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 4, 2003,
pp. 637 640.
Original Russian Text Copyright
2003 by Makarenko, Trukhin, Berestovitskaya.
Reactions of , -Dibromo- -nitrostyrenes
with Acetylacetone and Ethyl Acetoacetate
S. V. Makarenko, E. V. Trukhin, and V. M. Berestovitskaya
Herzen Russian State Pedagogical University, St. Petersburg, Russia
Received January 24, 2002
Abstract The reactions of , -dibromo- -nitrostyrenes with acetylacetone and ethyl acetoacetate were
1
studied. The structures of the products were determined by H NMR, IR, and UV spectroscopy. The products
derived from acetylacetone were converted into copper chelates.
, -Dibromo- -nitrostyrenes are new representa-
tives of halonitroethenes [1 4]. A combination of a
double bond with three functional substituents not
only extends the synthetic potential of these com-
pounds but also imparts to them peculiar properties as
compared to monohalonitroethenes [5 12].
We found that , -dibromo- -nitrostyrenes I and
II readily react with CH acids (acetylacetone, ethyl
acetoacetate) in absolute methanol at 8 to 10 C
within 2.5 3 h to form (at the substrate : CH acid :
CH3ONa ratio of 1 : 2 : 2) bright yellow crystalline
compounds III VI.
p-XH4C6
C=CHNO2
C(O)R
H2C
p-XH4C6
Br
C
R
H3C
C(O)CH3
C
O
C
O
C=C
CH3ONa
Br
NO2
H
I, II
III VI
X = H (I), Cl (II); R = CH3 (III, IV), OC2H5 (V, VI).
According to the concept of [13 15], the reaction
at the methylene group [19], is absent. Along with a
broad band of C H stretching vibrations at 3020
pathway can be considered as initial addition elimina-
tion (SNVin reaction) followed by substitution of the
positively polarized halogen by proton. Such a path-
way is nontrivial, although similar examples of halo-
gen reduction are known [15 18].
1
3010 cm , there are weak OH vibration bands at
1
3120 2830 cm . Such a pattern is characteristic of
the chelate structure of acetylacetone, acetoacetic acid
esters, and their monosubstituted derivatives with an
intramolecular hydrogen bond [19]. Conjugated car-
bonyl and the multiple bond in the spectra of V and
VI are manifested as broad strong bands at 1650 and
1
The IR, H NMR, and UV spectra confirmed the
structure of III VI (see table); the physicochemical
characteristics of the simplest representatives of this
series, III and V, coincided with those of the same
products prepared previously from -halo- -nitro-
styrenes [13, 14].
1
1610, 1590 cm . In the spectra of III and IV, the
bands of the carbonyl group and double bond overlap,
forming a broad strong ill-resolved band at 1610
1
1585 cm . So strong low-frequency shift of the car-
The IR spectra of III VI contain characteristic
absorption bands of antisymmetric and symmetric
stretching vibrations of the conjugated nitro group at
1515 1510 and 1335 1330 cm . However, the split
absorption band of the carbonyl stretching vibrations,
characteristic of 1,3-dicarbonyl compounds substituted
bonyl band is characteristic of compounds with a very
strong intramolecular hydrogen bond [20, 21], consid-
ered in some papers [22, 23] as a part of a pseudo-
aromatic system. Thus, the IR spectra of -nitroethen-
yldiacylmethanes III VI suggest that these compounds
chiefly exist in chloroform solutions in the enol form.
1
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MAKARENKO et al.
Spectral characteristics of III VI
1
IR spectrum (CHCl3), , cm
Comp.
1H NMR spectrum (CDCl3), , ppm
UV spectrum (CH3CN), , nm
1
no.
( , l mol 1 cm )
C=O, C=C
NO2
OH
CH3(C2H5)
Ph
=CH OH
III
IV
V
1605, 1590 1510, 1330 3115, 2850
1610, 1585 1515, 1335 3120, 2850
1650, 1610 1510, 1330 3105, 2830 1.74 (1.12, 4.16)
1650, 1610, 1515, 1330 3100, 2830 1.75 (1.11, 4.15)
1590
1.93
1.93
7.50 7.61 16.78 232 (6830), 287 (13470)
7.46 7.59 16.79 220 (9660), 287 (16150)
7.45
7.40
13.29 260 (10100), 294 309 (6300)
13.28 260 (12600), 298 307 (8400)
VI
1
This is also indicated by the H NMR spectra (see
table). For example, in the spectrum of III both meth-
yl groups, being magnetically equivalent, give a sin-
glet at 1.93 ppm. A down field signal at 16.78 ppm
can be assigned to the hydroxyl proton. A similar
spectral pattern is reported [24, 25] for the enol form
of acetylacetone. The phenyl and olefinic protons in
the spectrum of III give singlets at 7.50 and 7.61 ppm,
respectively.
the conjugated nitro group, also bands of the carbonyl
group and multiple bond, which are strongly shifted
toward lower frequencies and form a common broad
1
strong band at 1580 1560 cm , and characteristic
1
bands of the chelate ring at 1385 and 1365 cm . This
pattern is well consistent with the published data for
copper -diketonates [26].
Simple preparation of copper complexes VII and
VII and the possibility of considerably extending their
range by varying substituents in the benzene ring of
, -dibromo- -nitrostyrene open prospects for the
synthesis of a wide range of related chelates which
can be of interest for both basic (e.g., examination of
the transfer of electronic effects via metal ion) and
applied chemistry. It is known that chelates are widely
used as polymerization initiators and in analytical
chemistry and technology for extraction of metal ions;
many -diketonates exhibit laser activity [27, 28].
1
The H NMR spectra of V and VI virtually coin-
cide. The phenyl and olefinic protons in the spectrum
of V give a signal at 7.45 ppm, and the hydroxyl pro-
ton, at 13.29 ppm. The methyl and ethoxyl protons
give, respectively, a singlet at 1.74 ppm and multi-
plets at 1.12 and 4.16 ppm (see table).
The electronic spectra of III VI are consistent
with the suggested structure. Two absorption bands
are observed with
220 260 nm ( 6830
max 1
12600 l mol 1 cm ) and
287 309 nm (
1
To conclude, it should be emphasized that , -di-
bromo- -nitrostyrenes containing halogen atoms in
both geminal and vicinal positions relative to the nitro
group behave like vic-substituted, rather than gem-
substituted, monohalonitrostyrenes. Their reactions
with CH acids, as those with amines, follow the
SNVin pathway but are additionally accompanied by
reduction of the geminal halogen. The compounds
obtained by the reactions of , -dibromo- -nitrosty-
renes with acetylacetone can be recommended as con-
venient starting agents for preparing nitrovinyl-con-
taining chelates.
max 2
6300 16150 l mol 1 cm ).
1
The enol structure of III and IV is convincingly
confirmed by their tendency to form chelates. Copper
chelates VII and VIII are readily obtained by mixing
hot alcoholic solutions of III and IV with an aqueous
solution of copper acetate. Complexes VII and VIII
are green finely crystalline compounds readily crystal-
lizable from ethanol.
p-XH4C6
C=CHNO2
C
R
H3C
EXPERIMENTAL
(CH3COO)2Cu
alcohol,
2+ O
Cu
O
O
III, IV
O
The IR spectra were recorded on a Specord IR-75
spectrometer in chloroform or in KBr pellets in the
working ranges of LiF and NaCl prisms. The H
NMR spectra were recorded on a Bruker AC-200
spectrometer (200 MHz, internal reference TMS, sol-
vent CDCl3). The electronic absorption spectra were
measured on an SF-46 spectrophotometer in quartz
cells, solvent acetonitrile.
H3C
CH3
1
O2NCH=C
C6H4X-p
VII, VIII
The IR spectra of the copper complexes (see Exper-
imental) contain, along with the absorption bands of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 4 2003

REACTIONS OF , -DIBROMO- -NITROSTYRENES
605
1,2-Dibromo-1-nitro-2-phenyl- and -2-(p-chloro-
phenyl)ethenes I and II were prepared as described
in [2].
was filtered off. Yield of VI 0.4 g (32%); bright
yellow crystals, mp 69 71 C (from hexane). Found,
%: C 54.03, 54.02; H 4.62, 4.55; N 4.48, 4.50.
C14H15ClNO5. Calculated, %: C 53.84; H 4.84;
N 4.49.
3-Acetyl-5-nitro-4-phenyl-4-penten-2-one III.
A solution of 1.2 g of I in 10 ml of absolute methanol
was added dropwise at 5 to 10 C to a solution of
sodium acetylacetonate prepared from 0.8 ml of ace-
tylacetone and 0.18 g of sodium metal in 10 ml of
absolute methanol. The mixture was stirred at 5 to
10 C for 3 h, after which 0.45 ml of glacial acetic
acid was added, and the mixture was poured onto
crushed ice. The precipitate was filtered off. Yield of
III 0.44 g (45%); bright yellow crystals, mp 95 96 C
(from ethanol) (published data [14]: mp 96 C). Found,
%: C 63.24, 63.17; H 5.42, 5.40; N 5.64, 5.69.
C13H13NO4. Calculated, %: C 63.14; H 5.30; N 5.67.
3-Acetyl-5-nitro-4-phenyl-4-penten-2-one copper
chelate VII. A boiling solution of 2 g of copper(II)
acetate in 25 ml of distilled water was added to a boil-
ing solution of 0.25 g of III in 1 ml of ethanol. The
mixture turned dark green, and a finely dispersed
precipitate formed. After cooling, the precipitate was
filtered off and washed several times with hot water
to remove excess copper acetate. Yield of VII 0.29 g
(52%); green substance, mp 209 210 C (from ethan-
ol) (published data [14]: mp 209 210 C). IR spectrum
1
(KBr), , cm : 1580, 1520, 1385, 1325. Found, %:
C 56.02, 56.14; H 4.32, 4.35; N 5.03, 5.05. C26H24
CuN2O8. Calculated, %: C 56.11; H 4.32; N 5.04.
3-Acetyl-5-nitro-4-(p-chlorophenyl)-4-penten-2-
one IV. A solution of 0.68 g of II in 5 ml of absolute
methanol was added dropwise at 5 to 9 C to a solu-
tion of sodium acetylacetonate prepared from 0.4 ml
of acetylacetone and 0.09 g of sodium metal in 5 ml
of absolute methanol. The mixture was stirred at 5 to
9 C for 2.5 h, after which 0.2 ml of glacial acetic
acid was added, and the mixture was poured onto
crushed ice. The precipitate was filtered off. Yield
of IV 0.37 g (66%); bright yellow crystals, mp 113
114 C (from ethanol). Found, %: C 55.61, 55.54; H
4.50, 4.49; N 5.03, 5.04. C13H12ClNO4. Calculated,
%: C 55.51; H 4.30; N 4.98.
3-Acetyl-5-nitro-4-(p-chlorophenyl)-4-penten-2-
one copper chelate VIII. A boiling solution of 2 g of
copper(II) acetate in 25 ml of distilled water was
added to a boiling solution of 0.28 g of IV in 1 ml of
ethanol. The mixture turned dark green, and a finely
dispersed precipitate formed. After cooling, the pre-
cipitate was filtered off and washed several times with
hot water to remove excess copper acetate. Yield of
VIII 0.3 g (48%); green substance, mp 214 215 C
1
(from ethanol). IR spectrum (KBr), , cm : 1560,
1510, 1365, 1315. Found, %: C 50.09, 50.12; H 3.65,
3.66; N 4.51, 4.52. C26H22Cl2CuN2O8. Calculated, %:
C 49.97; H 3.55; N 4.48.
Ethyl 2-acetyl-4-nitro-3-phenyl-3-butenoate V.
A solution of 1.2 g of I in 10 ml of absolute
methanol was added dropwise at 5 to 8 C to a solu-
tion of sodium derivative of ethyl acetoacetate pre-
pared from 1 ml of ethyl acetoacetate and 0.18 g of
sodium metal in 10 ml of absolute methanol. The
mixture was stirred at 5 to 8 C for 3 h, after which
0.45 ml of glacial acetic acid was added, and the
mixture was poured onto crushed ice. The precipitate
was filtered off. Yield of V 0.48 g (43%); bright yel-
low crystals, mp 72 73 C (from hexane) (published
data [14]): mp 64 C). Found, %: C 60.42, 60.49; H
5.55, 5.51; N 5.01, 5.02. C14H16NO5. Calculated, %:
C 60.43; H 5.80; N 5.03.
ACKNOWLEDGMENTS
The study was financially supported by the Minis-
try of Education of the Russian Federation (project
no. E00-5.0-272).
REFERENCES
1. Makarenko, S.V., Trukhin, E.V., and Berestovits-
kaya, V.M., Zh. Org. Khim., 1998, vol. 34, no. 7,
p. 1112.
2. Berestovitskaya, V.M., Bel’skii, V.K., Macmil-
lan, G.H., Makarenko, S.V., and Trukhin, E.V., Zh.
Obshch. Khim., 1999, vol. 69, no. 5, p. 835.
3. Makarenko, S.V., Trukhin, E.V., Macmillan, G.H.,
and Berestovitskaya, V.M., Zh. Org. Khim., 1999,
vol. 35, no. 2, p. 330.
4. Ishmaeva, E.A., Berestovitskaya, V.M., Litvinov, I.A.,
Vereshchagina, Ya.A., Yarkova, E.G., Fattakho-
va, G.R., Krivolapov, D.B., Makarenko, S.V., Tru-
khin, E.V., and Pavlova, I.V., Zh. Obshch. Khim.,
2001, vol. 71, no. 3, p. 466.
Ethyl 2-acetyl-4-nitro-3-(p-chlorophenyl)-3-
butenoate VI. A solution of 1.37 g of II in 10 ml of
absolute methanol was added dropwise at 5 to 8 C
to a solution of sodium derivative of ethyl aceto-
acetate prepared from 1 ml of ethyl acetoacetate and
0.18 g of sodium metal in 10 ml of absolute methanol.
The mixture was stirred at 5 to 8 C for 3 h, after
which 0.45 ml of glacial acetic acid was added, and
the mixture was poured onto crushed ice. The yellow
oily precipitate crystallized on storage, after which it
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 4 2003

606
MAKARENKO et al.
5. Perekalin, V.V., Lipina, E.S., Berestovitskaya, V.M.,
18. Maffeo, C.V., Marchese, G., Naso, F., and Ronzini, L.,
and Efremov, D.A., Nitroalkenes. Conjugated Nitro
Compounds, New York: Wiley, 1994.
J. Chem. Soc., Perkin Trans. 1, 1979, no. 1, p. 92.
19. Neiland, O.Ya. and Vanag, G.Ya., Usp. Khim., 1959,
6. Trukhin, E.V., Makarenko, S.V., and Berestovits-
kaya, V.M., Zh. Org. Khim., 1998, vol. 34, no. 1,
p. 72.
vol. 28, no. 4, p. 436.
20. Bratoz, S., Hadzi, D., and Rossmy, G., Trans. Fa-
raday Soc., 1956, vol. 52, p. 464.
7. Sopova, A.S., Perekalin, V.V., and Yurchenko, O.I.,
21. Shigorin, D.N., Shemyakin, M.M., Shchukina, L.A.,
Kolosov, M.N., and Mendeleevich, F.A., Dokl. Akad.
Nauk SSSR, 1956, vol. 108, no. 4, p. 672.
Zh. Obshch. Khim., 1963, vol. 33, no. 7, p. 2140.
8. Sopova, A.S., Yurchenko, O.I., Perekalin, V.V., and
Tkhor, T.G., Zh. Org. Khim., 1971, vol. 7, no. 4,
p. 820.
22. Shigorin, D.N., Shcheglova, N.A., Dokunikhin, D.S.,
and Puchkov, V.A., Dokl. Akad. Nauk SSSR, 1960,
vol. 132, no. 6, p. 1372.
9. Yurchenko, O.I., Sopova, A.S., Perekalin, V.V., Beres-
tovitskaya, V.M., Polyanskaya, A.S., and Aboskalo-
va, N.I., Dokl. Akad. Nauk SSSR, 1966, vol. 171,
no. 5, p. 1123.
23. Oki, M., Hirota, M., and Hirofuji, S., Spectrochim.
Acta, 1966, vol. 22, no. 9, p. 1537.
24. Brand, J.C.D. and Eglinton, G., Applications of Spec-
troscopy to Organic Chemistry, London: Clarendon,
1960. ranslated under the title Primenenie spektrosko-
pii v organicheskoi khimii, Moscow: Mir, 1967,
pp. 84 85.
10. Metelkina, E.L., Sopova, A.S., and Ionin, B.I., Zh.
Org. Khim., 1972, vol. 8, no. 10, p. 2082.
11. Berestovitskaya, V.M., Sopova, A.S., and Pereka-
lin, V.V., Khim. Geterotsikl. Soedin., 1967, no. 3,
p. 396.
25. Roberts, J. and Caserio, M., Basic Principles of Or-
ganic Chemistry, New York: Benjamin, 1964. Trans-
ated under the title Osnovy organicheskoi khimii,
Moscow: Mir, 1968, part 1, pp. 438 439.
12. Sopova, A.S., Tkhor, T.G., Perekalin, V.V., and
Ionin, B.I., Zh. Org. Khim., 1972, vol. 8, no. 11,
p. 2301.
26. Junge, H. and Musso, H., Spectrochim. Acta (A), 1968,
13. Volynskii, V.E., Perekalin, V.V., and Sopova, A.S.,
vol. 24, no. 8, p. 1219.
Zh. Org. Khim., 1967, vol. 3, no. 7, p. 1345.
27. Rode, V.V., Rukhadze, E.G., and Terent’ev, A.P., Usp.
Khim., 1963, vol. 32, no. 12, p. 1488.
14. Volynskii, V.E., Perekalin, V.V., and Sopova, A.S.,
Zh. Org. Khim., 1970, vol. 6, no. 5, p. 938.
28. -Diketonaty metallov: Sbornik materialov II Vseso-
yuznogo seminara Stroenie, svoistva i primenenie
-diketonatov metallov (Metal -Diketonates: Coll.
of Papers of II All-Union Seminar Structure, Prop-
erties, and Applications of Metal -Diketonates ),
Moscow: Nauka, 1978.
15. Shainyan, B.A., Usp. Khim., 1986, vol. 55, no. 6,
p. 942.
16. Chanet-Ray, J. and Vessiere, R., Bull. Soc. Chim. Fr.,
1974, nos. 7 8, p. 1661.
17. Verny, M., Bull. Soc. Chim. Fr., 1970, no. 5, p. 1946.
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