Synthesis and properties of copper, mercury, and silver (2-naphthyl)acetylenides

Article abstract of DOI:10.1023/B:RUGC.0000031860.91216.62

(Z)-2-Naphthylacetylene was synthesized by the reaction of (Z)-3-(2-naphthyl)-3-chloropropenal (prepared from 2-acetylnaphthalene) with aqueous NaOH in dioxane. The reactions of 2-naphthylacetylene with CuCl, [Ag(NH₃)₂]NO₃, and K₂[HgI ₄] gave copper, silver, and mercury 2-naphthylacetylenides, respectively. Silver naphthylacetylenide reacts with iodine to give the iodoethynyl derivative, which readily takes up bromine across the triple bond.

Full text of DOI:10.1023/B:RUGC.0000031860.91216.62

Russian Journal of General Chemistry, Vol. 74, No. 4, 2004, pp. 578 581. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 4, 2004,
pp. 633 636.
Original Russian Text Copyright
2004 by Dikusar, Potkin, Vashkevich, Kozlov, Kaberdin.
Synthesis and Properties of Copper, Mercury,
and Silver (2-Naphthyl)acetylenides
E. A. Dikusar, V. I. Potkin, E. V. Vashkevich, N. G. Kozlov, and R. V. Kaberdin
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, Belarus
Received October 22, 2002
Abstract (Z)-2-Naphthylacetylene was synthesized by the reaction of (Z)-3-(2-naphthyl)-3-chloropropenal
(prepared from 2-acetylnaphthalene) with aqueous NaOH in dioxane. The reactions of 2-naphthylacetylene
with CuCl, [Ag(NH3)2]NO3, and K2[HgI4] gave copper, silver, and mercury 2-naphthylacetylenides, respec-
tively. Silver naphthylacetylenide reacts with iodine to give the iodoethynyl derivative, which readily takes up
bromine across the triple bond.
Naphthalene derivatives are widely used in syn-
thesis of dyes, pesticides, and drugs [1, 2]. One of
convenient routes to naphthalene functional deriva-
tives is introduction of the ethynyl group into the side
chain of the naphthalene system [3], followed by syn-
thesis of highly reactive metal acetylenides [4, 5].
cessible 2-acetylnaphthalene I. First, we prepared
(Z)-3-(2-naphthyl)-3-chloropropenal II by Vilsmeier
Haack formylation of ketone I. We were able to iso-
late and identify the intermediate reaction product,
3-(2-naphthyl)-3-chloro-2-propen-1-yl-N,N-dimethyl-
immonium chloride III (yield 90%), whose treatment
with sodium acetate in aqueous solution gave naph-
thylchloropropenal II in 72% yield (see scheme
below).
The goal of this work was synthesis of copper,
mercury, and silver 2-naphthylacetylenides from ac-
PCl5/HC(O)NMe2
Me
Cl
O
+
N(CH3)2
I
III
Cl
AcONa,
H2O
aqueous NaOH
dioxane
Cl
II
O
K2[HgI4]
IV
[Ag(NH3)2]NO3
CuCl
Cu
Ag
Hg
2
V
VI
VII
I2, CHCl3
Br
Br2, CH2Cl2
>
<
>
<
I
>
<
>
<
I
Br
IX
VIII
1070-3632/04/7404-0578 2004 MAIK Nauka/Interperiodica

SYNTHESIS AND PROPERTIES OF COPPER, MERCURY, AND SILVER
579
The compositions and structures of II and III were
determined by elemental analysis, IR and H spectros-
Acetylenides V VII are stable in storage at 0 5 C in
the dark.
1
copy, and mass spectrometry. In the IR spectra of II
and III, the C=C stretching vibrations are manifested
Acetylenides V VII were identified by IR spectros-
copy and elemental analysis. These compounds are
virtually insoluble in acetone, chloroform, benzene,
methanol, dimethyl sulfoxide, other organic solvents,
and also in water, and therefore we failed to record
1
1
at 1505 1624 cm . A strong band at 1645 cm in
the spectrum of III corresponds to the C=N bond.
The C=O vibrations in II give rise to a strong band at
1
1668 cm .
1
their H NMR spectra. In the IR spectra of V VII,
1
In the H NMR spectra of II and III, the signals of
the C H absorption band of the starting naphthyl-
acetylene IV is absent. The C C absorption band is
not manifested in the spectrum of copper naphthylace-
tylenide V; in the spectra of the silver and mercury
aromatic protons (multiplet) and exocyclic CCl=CH
group appear at 6.80 8.20 ppm. The singlet at 8.31
and 8.75 ppm for II and III, respectively, corresponds
to the C1H fragment of the naphthalene system. The
doublets at 10.27 ppm in the spectrum of III and
9.10 ppm in the spectrum of II are due to CH=N and
CH=O protons, respectively.
1
derivatives, it is observed at 2037 and 2142 cm ,
respectively.
Silver naphthylacetylenide VI was subsequently
used to prepare exocyclic halo derivatives. The reac-
tion of VI with iodine in chloroform gave 2-naphthyl-
ethynyl iodide VIII in 91% yield. Compound VIII
readily took up bromine in dichloromethane to form
dibromo iodide IX. A GC MS study showed that
compound IX was formed as a 3.5 : 1 mixture of the
E and Z isomers. The spectroscopic and analytical
data for VIII and IX are given in the Experimental.
3
The J coupling constants for the protons of the
side chain, equal to 7.7 and 9 Hz for II and III, re-
spectively, are indicative of the s-cis arrangement of
these hydrogen atoms [7]. Chakraborty and Ray [8]
studied the isomeric composition of aldehydes ob-
tained by the Vilsmeier Haack reaction from a series
of ketones, including 2-acetonaphthone I, and ob-
tained naphthylchloropropenal II exclusively in the
form of the Z isomer. Our data show that naphthyl-
substituted immonium chloride III and aldehyde II
have the s-cis-Z configuration of the side chain.
EXPERIMENTAL
The IR spectra were recorded on a Nikolet Protege-
1
460 Fourier spectrometer (KBr pellets). The H NMR
The mass spectrum of III contains isotopic peaks
of the [M Cl]+ ion, and the mass spectrum of II,
strong peaks of the molecular ion. The 35Cl/37Cl iso-
tope ratio in the peaks of the molecular ion of II,
equal to 100 : 33, indicates that the molecule of II
contains one chlorine atom [9, 10].
spectra were taken on a Tesla BS-567A spectrometer
in CDCl3, internal reference TMS. The mass spectra
were obtained on an MKh-1320 high-resolution mass
spectrometer at the ionizing electron energy of 50 eV.
The GC MS analysis of IX was performed on a Hew-
lett Packard GC/MS-5890/5972 device by the EPA
8270 method. The mercury content was determined
according to [11].
Treatment of II in dioxane with aqueous NaOH
gave 2-naphthylacetylene IV in 35% yield; its struc-
1
ture was confirmed spectroscopically. In the H NMR
3-(2-Naphthyl)-3-chloro-2-propen-1-yl-N,N-di-
methylimmonium chloride III. To 134 ml of dimeth-
ylformamide, we added 50.2 g of PCl5 in portions at
25 30 C over a period of 30 min. The mixture was
stirred for 2.5 3 h at 20 25 C and allowed to stand
for 8 h. To the resulting suspension of the Vilsmeier
Haack complex, a solution of 33 g of 2-acetonaph-
thone in 82.5 ml of dimethylformamide was added at
25 30 C over a period of 30 min. On stirring and
heating to 35 40 C, a bright yellow precipitate
formed, which was filtered off, washed with water and
diethyl ether, and vacuum-dried. Immonium chloride
III was obtained; yield 48.9 g (90%), mp 168 170 C.
Found, %: C 64.50; H 4.93; Cl 25.68; N 4.89.
C15H15Cl2N. [M]+ 279. Calculated, %: C 64.30; H
5.40; Cl 25.30; N 5.00. M 280.19.
spectrum of IV, protons of the naphthalene residue
give a multiplet at 7.4 8.1 ppm. The broadened sin-
glet at 8.0 ppm belongs to the C1H proton of the
naphthalene core. The acetylenic proton at C12 (side
chain) gives a singlet at 3.16 ppm. The presence of
the C C bond is confirmed by a characteristic IR band
1
1
at 2100 cm and by the C H band at 3280 cm .
The C=C bond in the CBr=CBr fragment gives bands
1
at 1500 1595 cm . The mass spectrum of IV con-
tains molecular (m/z 152) and fragmentation peaks.
By the reactions of 2-naphthylacetylene IV with
CuCl, [Ag(NH3)2]NO3, and K2[HgI4], we prepared
copper, silver, and mercury acetylenides V VII, re-
spectively. The reactions occurred at room tempera-
ture; the desired acetylenides were obtained in 91
94% yields and did not require additional purification.
s-cis-3-(2-Naphthyl)-3-chloropropenal II. A 30-g
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 4 2004

580
DIKUSAR et al.
portion of 3-(2-naphthyl)-3-chloro-2-propen-1-yl-N,N-
dimethylimmonium chloride III was treated with heat-
ing and stirring with 10 g of aqueous sodium acetate.
The precipitate that formed after cooling was filtered
off, washed with water and diethyl ether, vacuum-
dried, and recrystallized from chloroform. Yield of II
16.7 g (72%), mp 62 63 C. Found, %: C 72.37; H
4.05; Cl 16.18. C13H9ClO. [M] 216. Calculated, %:
C 72.06; H 4.19; Cl 16.36. M 216.66.
hexane, washed with aqueous Na2S2O3, and dried
over MgSO4. The solvent was removed. Product VIII
was recrystallized from hexane and purified by col-
umn chromatography on Al2O3 (Brockmann grade II),
eluent hexane. Yield of VIII 0.6 g (91%), mp 198
1
199 C. IR spectrum, , cm : 2170 (C C), 1496,
1
1567, 1592, 1623 (C=C), 481 (CI). H NMR spec-
trum, , ppm: 7.39 7.84 m (6Harom), 7.95 br.s
(1Harom). Found, %: C 51.64; H 2.75; I 45.28. C12H7I.
Calculated, %: C 51.83; H 2.54; I 45.63. M 278.08.
2-Naphthylacetylene IV. A solution of 2 g of II in
18 ml of dioxane was added dropwise to a hot solu-
tion of 1 g of NaOH in 10 ml of water. The mixture
was refluxed for 6 h; after cooling, the solvent was
distilled off, the residue was diluted with water, and
the flaky precipitate was filtered off, washed with cold
methanol, and recrystallized from methanol. Com-
pound IV was obtained; yield 0.49 g (35%), mp 35 C.
Found, %: C 94.65; H 5.35. C12H8. [M]+ 152. Calcu-
lated, %: C 94.69; H 5.31. M 152.18.
2-Naphthyl-1,2-dibromoethynyl iodide IX. To a
solution of 2.78 g of VIII in 30 ml of methylene
chloride, we added in one portion 0.52 ml of bromine
at 20 23 C with stirring. After keeping for 24 h under
these conditions, the solution decolorized. The solvent
was removed, and the residue was recrystallized from
hexane. Yield of IX 3.63 g (83%), mp 38 39 C. IR
1
spectrum, , cm : 1502, 1574, 1596, 1624 (C=C),
1
670 (CBr), 475 (CI). H NMR spectrum, , ppm:
7.44 7.89 m (7Harom). Found, %: C 33.12; H 1.86;
Hlg 65.38. C12H7Br2I. Calculated, %: C 32.91; H
1.61; Hlg 65.47. M 437.90.
Copper 2-naphthylacetylenide V. To a solution
of 0.4 g of CuCl and 0.5 g of hydroxylamine hydro-
chloride in a mixture of 1 g of water, 3 ml of mono-
ethanolamine, and 20 ml of methanol, we added in
one portion 0.4 g of 2-naphthylacetylene IV. The mix-
ture was stirred for 3 h at 20 23 C and diluted with
100 ml of water. The product was filtered off on a
glass frit, washed with a large amount of water, and
vacuum-dried in the dark. Yield of V 0.6 g (91%),
mp 260 C. Found, %: C 67.30; H 3.48; Cu 29.83.
C12H7Cu. Calculated, %: C 67.12; H 3.28; Cu 29.60.
M 214.72.
ACKNOWLEDGMENTS
The study was financially supported by the Bela-
russian Republican Foundation for Basic Research
(project no. Kh 00-045).
REFERENCES
1. Donaldson, N.D., The Chemistry and Technology of
Naphtalene Compounds, London: Arnold, 1958.
Silver 2-naphthylacetylenide VI. To a solution of
0.6 g of AgNO3 in 20 g of water and 5 g of 25%
aqueous NH4OH, we added in one portion 0.4 g of IV
in 10 g of dioxane. The subsequent synthesis was per-
formed similarly to V. Yield 94%, mp 170 C. Found,
%: C 55.42; H 2.99; Ag 41.72. C12H7Ag. Calculated,
%: C 55.63; H 2.73; Ag 41.64. M 259.05.
2. Mel’nikov, N.N., Khimiya i tekhnologiya pestitsidov
(Chemistry and Technology of Pesticides), Moscow:
Khimiya, 1974.
3. Bodendorf, K. and Mayer, R., Chem. Ber., 1965,
vol. 98, p. 3554.
Mercury 2-naphthylacetylenide VII. To a mix-
ture of 2.5 ml of Thoulet solution (saturated aqueous
K2[HgI4]), 4 g of KOH, and 35 g of water, we added
in one portion 0.4 g of IV in 10 ml of dioxane. The
subsequent synthesis was performed similarly to V.
Yield 92%, mp 170 171 C. Found Hg, %: 39.92.
C24H14Hg. Calculated, %: C 57.31; H 2.81; Hg 39.88.
M 502.94.
4. Dikusar, E.A., Koval’skaya, S.S., Vashkevich, E.V.,
Kozlov, N.G., Potkin, V.I., and Moiseichuk, K.L.,
Zh. Obshch. Khim., 1999, vol. 69, no. 11, p. 1809.
5. Dikusar, E.A., Kozlov, N.G., Koval’skaya, S.S., Po-
pova, L.A., and Moiseichuk, K.L., Zh. Obshch. Khim.,
2001, vol. 71, no. 2, p. 320.
6. Dikusar, E.A., Yuvchenko, A.P., Vashkevich, E.V.,
Kozlov, N.G., Potkin, V.I., and Moiseichuk, K.L., Zh.
Org. Khim., 1999, vol. 35, no. 3, p. 396.
2-Naphthylethynyl iodide VIII. To a suspension
of 0.78 g of VI in 20 ml of chloroform, we added in
one portion 0.78 g of iodine at 20 23 C with stirring.
The mixture was stirred at 20 23 C for 5 h and al-
lowed to stand for 15 18 h, after which the solution
was filtered to remove AgI, diluted with 50 ml of
7. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion. A Handbook of Practical Data, Techniques,
and References, New York: Wiley, 1972. Translated
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SYNTHESIS AND PROPERTIES OF COPPER, MERCURY, AND SILVER
581
under the title Sputnik khimika, Miscow: Mir, 1976,
10. Takhistov, V.V., Rodin, A.A., and Maksimova, B.N.,
p. 302.
Usp. Khim., 1991, vol. 60, no. 10, p. 2143.
8. Chakraborty, A. and Ray, J., Synth. Commun., 1995,
11. Hillebrand, W.F. and Lundell, G.E.F., Applied Inor-
ganic Analysis with Special Reference to the Analysis
of Metals, Minerals, and Rocks, New York: Wiley,
1953, 2nd ed. Translated under the title Prakticheskoe
rukovodstvo po neorganicheskomu analizu, Moscow:
Khimiya, 1960, p. 223.
vol. 25, no. 12, p. 1869.
9. Takhistov, V.V., Prakticheskaya mass-spektrometriya
organicheskikh soedinenii (Practical Mass Spec-
trometry of Organic Compounds), Leningrad: Leningr.
Gos. Univ., 1977.
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