9366
L.M. Mascavage et al. / Tetrahedron 64 (2008) 9357–9367
1; (e) Stroh, R. Methoden Org. Chem. (Houben-Weyl) 1962, 3, 812; (f) de la Mare, P.
trans-1-chloro-1,3-butadiene:
d 6.35–6.29 (1H, m); 6/25 (1H, m,
B. D.; Bolton, R. Electrophilic Additions to Unsaturated Systems; Elsevier: New York,
NY, 1966; pp 51–72; de la Mare, P. B. D.; Bolton, R. Electrophilic Additions to
Unsaturated Systems, 2nd ed.; Elsevier: New York, NY, 1982; pp 63–80; (g)
Mascavage, L. M.; Dalton, D. R. Trends Org. Chem. 1993, 4, 303–333; (h) Modern
Acetylene Chemistry; Stang, P. J., Diederich, F., Eds.; VCH: New York, NY, 1995;
pp 10–11.
partial overlapping with the cis-isomer); 5.49 (1H, dd, J¼17.3 Hz,
J¼10.8 Hz); 5.26 (1H, d, J¼16.8 Hz); 5.15 (1H, d, J¼10.2 Hz).
6.2.5. 4-Deutero-1-butene-3-yne (4-[2H1]-vinylacetylene)
The method of Tørneng et al.42 was modified. All glassware was
freshly annealed, cooled, and promptly assembled. A three-neck
round bottomed flask was equipped with a jacketed cold well
condenser (dry ice/acetone) connected to an oil bubbler, a septum
cap and nitrogen inlet. Under a positive nitrogen pressure, freshly
distilled THF (10 mL) and magnesium (2.03 g; 84.6 mmol) were
introduced into the flask, with stirring, followed by injection of
ethyl bromide (4 mL; 53.6 mmol). The reaction quickly occurred at
room temperature. After additional ethyl bromide (2.32 mL;
31.1 mmol) was added dropwise, the oil bath temperature was
raised to 60 ꢁC to reflux the mixture. At the same time, purified
vinylacetylene was transferred to an evacuated tube equipped with
a Teflon stopcock and 10/30 joint. The vinylacetylene was placed in
an ice-water bath, the stopcock removed and nitrogen quickly in-
troduced through the 10/30 joint, and the stopcock opening capped
with a septum containing a gas outlet needle and a Teflon cannula.
Vinylacetylene was slowly introduced into the reaction flask
through the cannula; a vigorous reaction immediately occurred.
After the reaction subsided, the flask was cooled to room temper-
ature and the dry ice/acetone condenser was replaced with a water
condenser connected to a trap at ꢀ78 ꢁC to collect the product. The
nitrogen flow was reduced to about one bubble per second and D2O
(99.9%; 15.3 ml; 84.6 mmol) was added dropwise with a syringe.
After the addition was completed the trap with the 4-deutero-1-
butene-3-yne was connected to the vacuum rack and degassed
using three freeze-thaw cycles. Both the 1H NMR and the GC
showed the presence of ethyl bromide and some low boiling im-
purity. Further purification was achieved by trap (ꢀ78 ꢁC) to trap
(liquid nitrogen) distillation, which was monitored by analytical GC
and 1H NMR. After discarding the low boiling impurity and the high
boiling fraction containing water and ethyl bromide, the 4-deutero-
1-butene-3-yne was stored in an evacuated 5 L bulb attached to the
vacuum rack. Integration of the 1H NMR showed that 90% of the
2. The following list is incomplete. It is provided as representative only and in-
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d 5.83; 5.82;
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Acknowledgements
L.M.M. gratefully acknowledges the Beaver College (Arcadia
University) Faculty Development Award for partial financial sup-
port. We are grateful to Dr. H. Simmons III, Central Research and
Development, E.I. du Pont de Nemours & Company, Wilmington,
DE, for providing authentic 2-chloro-1,3-butadiene. We also ap-
preciate the expert technical assistance by Temple University’s Mr.
D. Plasket, Glassblower, and Mr. F. Mansell, Chemistry-Physics
Machine Shop.
19. Rettner, C. T.; Auerbach, D. J. Science 1994, 263, 365.
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Supplementary data
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Supplementary data associated with this article can be found in
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