60
DANILIN et al.
unsaturated diesters V and VI. O-Alkylation of car-
boxylic acids with -haloketone I results in formation
of 2-(1-adamantyl)-2-oxoethyl carboxylates VII, and
ethyl acetoacetate reacts with ketone I in HMPA
in the presence of metallic potassium to give ethyl
3-(1-adamantylcarbonylmethoxy)-2-butenoate (VIII).
of glacial acetic acid in 150 ml of benzene was re-
fluxed in a flask equipped with a Dean Stark trap.
When water no longer separated (after 2.5 6 h), the
mixture was cooled to room temperature, and the
benzene layer was washed with four small portions of
a semisaturated solution of sodium chloride, dried
over sodium sulfate, and evaporated. The residue was
recrystallized from ethanol diethyl ether (5:1).
EXPERIMENTAL
2-(1-Adamanyl)-2-oxoethyl carboxylates VIIa
VIIe. A mixture of 0.5 g (1.9 mmol) of bromoketone
I, 18 mmol of carboxylic acid, and 11 mmol of tri-
ethylamine in 10 ml of acetone was refluxed for
6 12 h. A colorless solid (triethylamine hydro-
bromide) separated during the process. The mixture
was poured into water, and the precipitate was filtered
off, washed with a 10% solution of sodium hydroxide,
and recrystallized from hexane.
Ethyl 3-(1-adamantylcarbonylmethoxy)-2-buten-
oate (VIII). Metallic potassium, 1.15 g (3.9 mmol),
was added with stirring to 20 ml of hexamethylphos-
phoramide. Ethyl acetoacetate was then added drop-
wise at 20 C. The mixture was stirred for 10 min at
room temperature and for 10 h at about 100 C. It
was then cooled to 20 C, and a solution of 1 g
(3.89 mmol) of bromoketone I in 10 ml of HMPA
was added with stirring over a period of 20 min. The
mixture was stirred for 30 min at 20 C and for 5 h
at 100 C, diluted with a tenfold amount of water, and
extracted with ether (3 100 ml). The extracts were
washed with water and dried over sodium sulfate. The
solvent was distilled off to leave a yellow oily sub-
stance which crystallized on treatment with methanol.
1
The H NMR spectra were recorded on a Bruker
AC-300 instrument (300.13 MHz) in DMSO-d6 with
HMDS as internal reference. The IR spectra were
measured on a Specord M-80 spectrometer in KBr.
The purity of the products was checked by TLC on
Silufol UV-254 plates; the chromatograms were
developed with iodine vapor.
3-(1-Adamantylcarbonylmethyl)-2,4-pentane-
dione (IIIa) and 4-acetyl-1-(1-adamantyl)-2,5-
hexanedione (IVa). Metallic sodium, 3.9 mmol, was
added in small pieces to a mixture of 15 ml of dry
diethyl ether and 15 ml of anhydrous methanol, stirred
at 20 C. The mixture was stirred for 15 min, and
3.9 mmol of acetylacetone was added dropwise with
stirring over a period of 10 15 min. The mixture was
stirred for 30 min at 20 C and for 2 h under reflux.
It was then cooled to room temperature, a solution of
3.89 mmol of haloketone I or II in 20 ml of dry
diethyl ether was added, and the mixture was stirred
for 30 min at 20 C and for 30 min under reflux. The
solvent was distilled off, the product was extracted
into ether, the extract was washed with a small
amount of water, dried over sodium sulfate, and
evaporated, and the residue was recrystallized from
ethanol.
REFERENCES
Ethyl 2-(1-adamantylcarbonylmethyl)-3-oxobut-
anoate (IIIb) and ethyl 2-acetyl-5-(1-adamantyl)-4-
oxopentanoate (IVb). Ethyl acetoacetate, 3.89 mmol,
was added with stirring over a period of 30 min to
a suspension of 3.9 mmol of metallic sodium in 40 ml
of dry diethyl ether, and the mixture was heated for
about 3 h until sodium dissolved completely. A solu-
tion of 3.89 mmol of haloketone I or II in 30 ml
of dry diethyl ether was then added over a period
of 40 min, the mixture was heated for 6 7 h, and
30 ml of water was added on cooling. The organic
phase was separated, dried, and evaporated, and the
crude product was recrystallized from a small amount
of methanol.
1. Makarova, N.V., Zemtsova, M.N., and Moiseev, I.K.,
Khim. Geterotsikl. Soedin., 1994, no. 5, pp. 621 623.
2. Tadashi, S., Shoji, E., and Takeshi, T., Bull. Chem.
Soc. Jpn., 1969, vol. 42, no. 6, pp. 1617 1621.
3. Stepanov, F.N. and Isaev, S.D., Zh. Org. Khim., 1970,
vol. 6, no. 6, pp. 1195 1198.
4. Makarova, N.V., Zemtsova, M.N., and Moiseev, I.K.,
Khim. Geterotsikl. Soedin., 1993, no. 11, pp. 1579
1580.
5. Makarova, N.V., Zemtsova, M.N., and Moiseev, I.K.,
Khim. Geterotsikl. Soedin., 1994, no. 2, pp. 249 252.
6. Nakayama, J., Hasemi, R., and Yoshimura, K., J. Org.
Chem., 1998, vol. 63, no. 15, pp. 4912 4924.
Diethyl 1-(1-adamantyl)-2-bromoethylidene-
malonate (V) and diethyl 1-(1-adamantylmethyl)-
2-bromoethylidenemalonate (VI). A mixture of
0.5 mol of haloketone I or II, 0.5 mol of diethyl
malonate, 0.05 mol of ammonium acetate, and 0.1 mol
7. Lauria, F., Vecchietti, V., and Bergamaschi, M.,
Farmaco, Ed. Sci., 1967, vol. 22, no. 9, pp. 681 691.
8. Novikova, M.I., Isaev, S.D., and Kazan’uk, L.V.,
Abstracts of Int. Conf. Alkane Activation and Cage
Compounds Chemistry, Kiev, Ukraine, 1998, B-38.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 1 2001
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