Abstract
Nitroacetylene (1 ) was prepared by the
reaction of NO2 PF6 with trimethylsilylacetylene.
It is stable at room temperature in dilute solution for about a
week. The 1 H and 13 C
NMR spectra of nitroacetylene reveal strong 1 H-14 N
and 13 C-14 N
spin couplings. Nitroacetylene reacts rapidly with nucleophiles.
It gives a 1,4-Diels-Alder adduct with cyclopentadiene.
However, its reactions with furan and vinyl ethers produce nitrovinylisoxazoles
by a mechanism thought to involve the 1,4-addition of nitroacetylene
to the vinyl ether to give a highly strained unsaturated nitrone,
followed by fragmentation of the nitrone to vinyl nitrile oxide,
then additions of this 1,3-dipolarophile.
Key words
nitroacetylene - alkynes - Diels-Alder
reactions - vinyl nitrile oxide - isoxazoles - heterocylcles
References
1a </A>
Eaton PE.
Gilardi RL.
Zhang M.-X.
Adv. Mater.
2000,
12:
1143
1b </A>
Zhang M.-X.
Eaton PE.
Gilardi R.
Angew.
Chem. Int. Ed.
2000,
39:
401
<A NAME="RC03402SS-2">2 </A>
Politzer P.
Lane P.
Wiener JJM.
Carbocyclic and Heterocyclic Cage Compounds
and Their Building Blocks
Laali K.
JAI
Press;
Stamford:
1999.
p.73
<A NAME="RC03402SS-3">3 </A>
Rall KB.
Vil’avskaya AI.
Petrov AA.
Russ. Chem. Rev.
1975,
44:
373
<A NAME="RC03402SS-4">4 </A>
Jäger V.
Viehe HG.
Angew. Chem., Int.
Ed. Engl.
1969,
8:
273
5a </A>
Motte JC.
Viehe HG.
Chimia
1975,
29:
515
5b </A>
Jager V.
Motte JC.
Viehe HG.
Chimia
1975,
29:
516
5c </A>
Petrov AA.
Zavgorodnii VS.
Rall KB.
Vil’davskaya AI.
Bogoradovskii ET.
Zh.
Obshch. Khim.
1978,
48:
943
6a </A>
Schmitt RJ.
Bedford CD.
Synthesis
1986,
132
6b </A>
Schmitt RJ.
Bottaro JC.
Malhotra R.
Bedford CD.
J.
Org. Chem.
1987,
52:
2294
6c </A>
Bottaro JC.
Schmitt RJ.
Bedford CD.
Gilardi R.
George C.
J. Org. Chem.
1990,
55:
1916
7a </A>
Politzer P.
Bar-Adon R.
J.
Am. Chem. Soc.
1987,
109:
3529
7b </A>
Tomonari M.
Ookubo N.
THEOCHEM
1998,
451:
179
7c </A>
Egorochkin AN.
Skobeleva SE.
Mushtina TG.
Bogoradovsky ET.
Russ.
Chem. Bull.
1998,
47:
1526
7d </A>
Nguyen LT.
De Proft F.
Chandra AK.
Uchimaru T.
Nguyen MT.
Geerlings P.
J.
Org. Chem.
2001,
66:
6096
8 </A>
We have recently had some success using
nitronium triflate, an easily purified material.
<A NAME="RC03402SS-9">9 </A>
Berger S.
Braun S.
Kalinowski H.-O.
NMR Spectroscopy of the Non-metallic Elements
Wiley;
New
York:
1996.
p.398
<A NAME="RC03402SS-10">10 </A>
Lickiss PD.
The Chemistry of Organic Silicon Compounds
Vol.
2:
Rappoport Z.
Apeloig Y.
Wiley;
New York:
1998.
p.557
11a </A>
Coburn MD.
Storm CB.
Moore DW.
Archibald TG.
Magn. Reson. Chem.
1990,
28:
16 ; and references therein
12a </A>
Eaton PE.
Stubbs CE.
J. Am. Chem. Soc.
1967,
89:
5722
12b </A>
Gilardi R.
Evans R.
Zhang M.-X.
Acta
Chryst.
2002,
E58:
856
<A NAME="RC03402SS-13">13 </A>
Keana JFW.
Little GM.
Heterocycles
1983,
20:
1291
<A NAME="RC03402SS-14">14 </A>
Diamantini G.
Duranti E.
Tontini A.
Synthesis
1993,
1104
<A NAME="RC03402SS-15">15 </A>
X-ray data for 10 have
been deposited with the Cambridge Crystallographic Data Centre (no.
187049).
<A NAME="RC03402SS-16">16 </A>
Denmark SE.
Thorarensen A.
Chem. Rev.
1996,
96:
137
<A NAME="RC03402SS-17">17 </A>
Wentrup C.
Gross G.
Maquestiau A.
Flammang R.
Angew. Chem., Int. Ed. Engl.
1983,
22:
542
<A NAME="RC03402SS-18">18 </A>
Torssell KBG.
Nitrile Oxides, Nitrones,
and Nitronates in Organic Synthesis
VCH;
New
York:
1988.
<A NAME="RC03402SS-19">19 </A>
Ref.
[18
<A NAME="RC03402SS-20">20 </A>
Caramella P.
Cellerino G.
Coda AC.
Invernizzi AG.
Grünanger P.
Houk KN.
Albini FM.
J. Org. Chem.
1976,
41:
3349
21a </A>
Rene L.
Royer R.
Synthesis
1981,
878
21b </A>
Kogan TP.
Gaeta FCA.
Synthesis
1988,
706
22 </A>
From the 14 N-decoupled, 1 H-coupled
spectrum.
