L. Cermenati et al. / Tetrahedron 59 (2003) 6409–6414
6413
3. Experimental
internal standards. Gas chromatographic analyses were
carried out by using an HP 5890 apparatus with a
0.3 mm£30 m capillary column with a flame ionization
detector. Gas chromatography/mass spectrometry deter-
mination was performed using an HP 5970B instrument
operating at a ionizing voltage of 70 eV, connected to
an HP 5890 instrument equipped with the same column
as above.
Reagents. Degussa P25 titanium dioxide was dried in a oven
at 1108C for 24 h and acetonitrile was distilled from calcium
hydride and stored over molecular sieves. The chemicals
used were either commercial compounds or were prepared
according to published procedures, as in the case of dinitrile
IPMN.17
Irradiations. A 140 mg sample of titanium dioxide (or a
lower amount, see Table 1) was weighted in a round
bottomed Pyrex tube (2.4 cm internal diameter, 14 cm
height). A solution of adamantane or other alkanes (0.01 or
0.02 M) with the appropriate additives in MeCN or CH2Cl2
(40 mL) was added. The tube was sealed with a serum cap
and the mixture sonicated for 1 min. Two needles were
inserted and either oxygen or purified nitrogen was passed
through the solution for 15 min with magnetic stirring. One
to four of such tubes were put in the center of four 15 W
phosphor-coated lamps (40 cm length, 350 nm center of
emission) and irradiated while maintaining a slow flux of
gas and magnetic stirring. The reaction course was
monitored by GC. The suspension was then filtered over a
0.2 mm porosity filter under vacuum. Samples were either
directly analyzed or rotary evaporated and taken up to a
fixed volume for quantitative determination (see below).
Several batches were reunited, evaporated and
chromatographed.
Larger scale irradiations were carried out with a suspension
of TiO2 (0.7 g) in MeCN (200 mL) in an immersion well
apparatus fitted with a Pyrex-filtered, water-cooled medium
pressure mercury arc (150 W). The suspension was
magnetically stirred and flushed with oxygen during
irradiation. GC analysis and preparative chromatographic
separation were carried out as above.
Acknowledgements
Partial support of this work by INCA, Venice, in the frame
of the program on sustainable chemistry is gratefully
acknowledged. DD thanks Solchem, Dorno for a research
fellowship.
References
The most abundant compounds were isolated by silica gel
chromatography (cyclohexane–ethyl acetate mixtures as
the eluant). 1- and 2-Adamantanol (1, 2), adamantanone (3)
and 2-(1-adamantyl)-etanone (6) were identified by com-
parison of their GC/MS and NMR spectra with commercial
authentic samples. N-(1-Adamantyl)acetamide (5) was
identical to a previously obtained sample10 and bicyclo-
[3.3.1]nonan-3,7-dione (4) was recognized on the basis of
the comparison of spectroscopic characteristics, in particu-
lar of 1H, 13C (DEPT) NMR spectra with a literature
report.18
1. (a) Fokin, A. A.; Schreiner, P. R. Chem. Rev. 2002, 102, 1551.
(b) In Activation and Functionalization of Alkanes; Hill, C. L.,
Ed.; Wiley: New York, 1989. (c) Olah, G. A.; Faroq, O.;
Prakash, G. S. K. Activation and Functionalization of Alkanes;
Wiley: New York, 1989. (d) Davies, J. A.; Watson, P. L.;
Liebman, G. F.; Greenberg, A. Selective Hydrocarbon
Activation; VCH: Weinheim, 1990. (e) Crabtree, R. H.
Chem. Rev. 1995, 95, 245.
2. (a) Maldotti, A.; Molinari, A.; Amadelli, R. Chem. Rev. 2002,
102, 3811. (b) Kisch, H. Adv. Photochem. 2001, 26, 93.
3. (a) Cardarelli, A. M.; Fagnoni, M.; Mella, M.; Albini, A.
J. Org. Chem. 2001, 66, 7320. (b) Mella, M.; Freccero, M.;
Albini, A. Tetrahedron 1996, 52, 5523. (c) Mella, M.;
Freccero, M.; Albini, A. Tetrahedron 1996, 52, 5549.
2-[1-(1-Adamantyl)-1-methyl)]ethylpropanedicarbonitrile
(8), colorless solid, mp 66–678C; analysis C 79.5, H 9.3, N
11.2 %, calculated for C16H22N2, C 79.29, H 9.15, N
11.56%; 1H NMR (CDCl3) d 1.2 (s, 6H, CH3), 1.6–1.8 (m,
12H, CH2), 2.1 (br, s, 3H, CH), 3.75 (s, 1H, a-CH); 13C
NMR (CDCl3) d 21.0 (CH3), 28.2 (CH), 30.2 (CH), 36.3
(CH2), 36.6 (CH2), 37.6, 43.0, 113.4 (CN); IR (melt)
2251 cm21; MS, m/e 242 (Mþ, 4%), 177 (10), 135 (100).
4. (a) Muzart, J.; Henin, F. C.R. Acad. Sci. Ser. 1988, 2,
307–479. (b) Cheng, J. Y. K.; Cheung, K. K.; Che, C. M.; Lau,
T. C. Chem. Commun. 1997, 1443. (c) Combs-Walker, L. A.;
Hill, C. L. J. Am. Chem. Soc. 1992, 114, 938. (d) Renneke,
R. F.; Kadkhodayan, M.; Pasquali, M.; Hill, C. L. J. Am.
Chem. Soc. 1991, 113, 8357. (e) Jaynes, B. S.; Hill, C. G.
J. Am. Chem. Soc. 1995, 117, 4704. (f) Zheng, Z.; Hill, C. G.
Chem. Commun. 1998, 2467. (g) Ermolenko, L. P.; Delaire,
J. A.; Giannotti, C. J. Chem. Soc., Perkin Trans. 2 1997, 25.
(h) Giannotti, C.; Richter, C. Int. J. Photoen. 1999, 1, 69.
(i) Duncan, D. C.; Fox, M. A. J. Phys. Chem. A 1998, 102,
4559. (j) Tanielian, C. Coord. Chem. Rev. 1998, 178, 1165.
(k) Kothe, T.; Martschke, R.; Fischer, H. J. Chem. Soc., Perkin
Trans. 2 1998, 503. (l) Molinari, A.; Amadelli, R.; Carassiti,
V.; Maldotti, A. Eur. J. Inorg. Chem. 2000, 1, 91.
In other cases, the amount was too low for a preparative
separation and the compound was identified by comparison
of the GC/MS characteristics with that of authentic samples,
either of commercial origin (1- and 2-chloroadamantane,
1-adamantenenitrile) or prepared through a known method
(1,1-diadamantane).19 The identification of 1, 2-hydroxy-
adamantane (7) was suggested on the basis of the MS
fragmentation that distinguished it from other isomers.20
1-Hydroxyadamantan-2-one was likewise recognized by
comparing GC/MS data with the literature.21
5. (a) Pichat, P.; Fox, M. A. In Photoinduced Electron Transfer;
Fox, M. A., Chanon, M., Eds.; Elsevier: Amsterdam, 1988; p
241. (b) Fox, M. A.; Dulay, M. T. Chem. Rev. 1993, 93, 341.
(c) Macyk, K.; Kisch, H. Chem. Eur. J. 2001, 7, 1862.
6. (a) Legrini, O.; Oliveros, E.; Braun, A. Chem. Rev. 1993, 93,
The yields were determined by GC on the basis of
calibration curves using dodecane or cyclododecane as the