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presence of a catalytic amount of triethylamine [Eq. (11)]. In
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In conclusion, cyanobutadiyne (2) was synthesized in pure
form by the reaction of the 1,3-butadiynyltributylstannane
with p-toluenesulfonyl cyanide. This approach paves the way
to the synthesis of other cyanopolyynes and the correspond-
ing isotopomers. According to our study, cyanobutadiyne can
possibly be formed on Titan or in the interstellar medium by
photolysis of mixtures of acetylene and cyanoacetylene or
dicyanoacetylene or mixtures of dicyanoacetylene and buta-
diyne. Compound 2 only undergoes 1,6-addition with nucle-
ophiles. The measurement of the gas-phase IR spectrum of a
pure sample of 2, the study of its photochemistry, and the
extension of this approach to other cyanopolyynes are
currently underway in our laboratory.
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Experimental Section
2: Two traps equipped with stopcocks were attached to a vacuum line.
1,3-Butadiynyltri-n-butylstannane (4; 0.54 g, 1.6 mmol) and p-tolu-
enesulfonyl cyanide (3; 0.90 g, 5.0 mmol) were introduced into a flask
equipped with a stirrer bar and the flask was attached to the vacuum
line. The flask was immersed in a bath and slowly warmed to 708C
over 1h. The cyanobutadiyne (2) formed was continuously removed
by distillation in vacuo from the reaction mixture. The first trap,
cooled at ꢀ308C, selectively removed the less-volatile products, and 2
(18 mg, 0.24 mmol, 15%) was selectively condensed in the second
[17] The formation of cyanoalkynes by reaction of an alkynyl
stannane with a ClCN–AlCl3 complex in dichloromethane has
already been reported.[10] However, purification with aqueous
HCl followed by flash chromatography is inappropriate for
kinetically unstable compounds.
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ꢀ
[20] The breaking of the H C bond of cyanoacetylene does not occur
trap cooled at ꢀ808C. IR (gas phase): n˜ = 642, 1272, 2190 (nC C), 2253
=
upon irradiation at wavelengths longer than 240 nm: D. W.
Clarke, J. P. Ferris, Icarus 1995, 115, 119 – 125.
(nC N), 3328 cmꢀ1 (nC-H); 1H NMR (CDCl3, 400 MHz, 298 K): d =
=
2.41 ppm; 13C NMR (CDCl3, 100 MHz, 298 K): d = 48.9 (4JC,H
<
[21] C. K. Ingold, G. W. King, J. Chem. Soc. 1953, 2704 – 2707; H.
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1 Hz; C2), 66.0 (2JC,H = 52.2 Hz; C4), 66.9 (3JC,H = 6.4 Hz; C3), 71.7
(1JC,H = 265.0 Hz; C5), 104.8 ppm (C1); HRMS: calcd for HC5N:
75.01090; found: 75.0109; MS: m/z (%): 76 (3.6), 75 (100), 74 (11.2),
50 (3.4), 49 (6.8).
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Received: June 18, 2005
Published online: October 17, 2005
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cyano- and the 1-haloacetylenes” H. Hopf, B. Witulski in
Modern Acetylene Chemistry (Eds: P. J. Stang, F. Diederich),
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Keywords: alkynes · cyanides · diynes · nucleophilic addition ·
photochemistry
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