1054
M. V. Raiman et al.
LETTER
added to the cooled solution, while stirring. The mixture is
References and Notes
keeped at –10°C for 15 hours. The reaction mixture is poured
into 200 ml of water, precipitated tosylate 4 is filtered off. The
product is washed with 3 ml of cooled hexane. 4: pinkish
crystals: mp 78°C. 1H NMR (60 MHz, CCl4): δ = 0.57 – 0.87
(m, 2 H); 0.98 - 1.28 (m, 2 H); 2.10 (s, 3 H); 2.41 (s, 3 H); 2.80
(s, 2 H); 7.12 – 7.80 (m, 4 H).
(1) Suckling, J. Angew. Chem. Int. Ed Engl. 1988, 27, 537.
Salaün, J., Baird, M. S. Curr. Med. Chem. 1995, 2, 511. Liu,
H.-W.; Walsh, C. T. in The Chemistry of Cyclopropyl group,
Ed. Z. Rappoport 1987, 959. Salaün, J. Zh. Org. Khim. 1997,
33, 806; Russ. J. Org. Chem. 1997, 33, 742.
(2) Wong, H. N. C.; Hon, M. Y.; Tse, C.-W.; Yip, Y. C.; Tanko,
J; Hudlicky, T. Chem. Rev. 1989, 89, 165. Reissig, H.-U. in
The Chemistry of Cyclopropyl group, Ed. Z. Rappoport 1987,
375. Lee, J.; Kim, H.; Cha, J. K. J. Am. Chem. Soc. 1996, 118,
4198. Lee, J.; Kim, Y. G.; Bae, J. G.; Cha, J. K. J. Org. Chem.
1996, 61, 4878. Lee, J., Cha, J. K. J. Org. Chem. 1997, 62,
1584. Chaplinski, V., de Meijere, A. Angew. Chem. Int. Ed.
Engl. 1996, 35, 413. Chaplinski, V.; Winsel, H.; Kordes, M.;
de Meijere, A. Synlett 1997, 111.
(3) Aufranc, P.; Ollivier, J.; Bremer, C.; Es-Sayed, M.; de
Meijere, A.; Salaün, J. Tetrahedron Lett. 1993, 34, 4193.
Atlan, V.; Racouchot, S.; Rubin, M.; Bremer, C.; Ollivier, J.;
de Meijere, A.; Salaün, J. Tetrahedron: Assymetry 1998, 9,
1131.
(4) Van Tilborg, V. J. M.; Dooyewaard, G.; Steinberg, H.; de
Boer, Th. J. Tetrahedron Lett. 1972, 1677.
(5) Kulinkovich, O. G.; Sviridov, S. V.; Vasilevskii, D. A.;
Pritytskaya, T. S. J. Zh. Org. Khim. 1989, 25, 2244; J. Org.
Chem. USSR 1989, 25, 2027. Kulinkovich, O. G.; Sviridov, S.
V.; Vasilevskii, D. A. Synthesis 1991, 234.
(10) A solution of 4 mmol of compound 4 and 16 mmol of amine
in 20 ml of dry benzene is stirred at room temperature for an
hour. Precipitate is filtered off and the solvent is evaporated.
Gaseous amines are passed trough the solution of compound 4
in benzene for 15 minutes, then the reaction mixture is keeped
at room temperature for 45 minutes. Aminocyclopropanes
(6a-h) are isolated by distillation at reduced pressure or, in the
case of unstable compound 6 i, by column chromatography. 6
a: colourless liquid: bp 80°C (30 mm Hg); 1H NMR (60 MHz,
CDCl3): δ = 0.20-0.33 (m, 2 H); 0.40 – 0.53 (m, 2 H); 1.90 (s,
3 H); 2.10 (s, 3 H); 2.27 (s, 2 H).- 6 b: colourless liquid: bp 40-
44°C (2 mm Hg); 1H NMR (60 MHz, CCl4): δ = 0.30 – 0.46
(m, 2 H); 0.56 - 0.73 (m, 2 H); 1.90 (s, 3 H); 2.03 (s, 1 H); 2.43
(s, 2 H); 3.67 (s, 2 H); 7.23 (m, 5 H). – 6 c: colourless liquid:
bp 65-66°C (16 mm Hg); 1H NMR (60 MHz, CCl4): δ = 0.28
– 0.40 (m, 2 H); 0.50 - 0.63 (m, 2 H); 0.93 (d, 6 H; J = 6 Hz);
1.78 (s, 1 H); 2.03 (s, 3 H); 2.38 (s, 2 H); 2.67 – 3.13 (m, 1 H).-
6 d: colourless liquid: bp 43°C (2 mm Hg); 1H NMR (250
MHz, CDCl3): δ = 0.27 - 0.40 (m, 2 H); 0.53–0.67 (m, 2 H);
1.05 (s, 9 H); 2.00 (s, 3 H); 2.47 (s, 2 H); 2.70 (s, 1 H).- 6 e:
colourless liquid: bp 65-66°C (10 mm Hg); 1H NMR (60
MHz, CCl4): δ = 0.40 – 0.60 (m, 4 H); 2.04 (s, 3 H); 2.13 (s, 6
H); 2.33 (s, 2 H).-6 f: colourless liquid: bp 33°C (2 mm Hg);
1H NMR (60 MHz, CCl4): δ = 0.40-0.63 (m, 4 H); 0.97 (t, 6 H,
J = 7 Hz); 2.03 (s, 3 H); 2.27 – 2.70 (m, 6 H). - 6 g: colourless
liquid: bp 90°C (2 mm Hg); 1H NMR (60 MHz, CCl4):
δ = 0.47 – 0.7 (m, 4 H); 2.10 (s, 3 H); 2.37 – 2.60 (m, 6 H);
3.37 – 3.63 (m, 4 H). - 6 h: colourless liquid: bp 55-56°C (2
mm Hg); 1H NMR (60 MHz, CCl4): δ = 0.47-0.70 (m, 4 H);
1.30-1.60 (m, 6 H); 2.13 (s, 3 H); 2.45 (s, 2 H); 2.45- 2.67 (m,
4 H). - 6 i: colourless liquid: SiO2, hexane-ether = 1:2;
1H NMR (60 MHz, CCl4): δ = 0.53 – 0.66 (m, 2 H); 0.77 - 0.90
(m, 2 H); 1.93 (s, 3 H); 2.57 (s, 2 H); 4.37 –4.67 (m, 1 H); 6.50
– 7.10 (m, 5 H).
(6) All new compounds were characterized by spectroscopic
methods (IR, NMR) and their molecular formulas confirmed
by elemental analysis. Synthesis of compound 2: A solution of
62.5 mmol of ethylmagnesium bromide in a mixture of 10 ml
of tetrahydrofuran and 30 ml of diethyl ether is added to a
solution of 25 mmol of acetoacetic ester ethylene acetal 1 and
5 mmol of titanium (IV) isopropoxide in 60 ml of
tetrahydrofuran in the course of 2 hours at a temperature of 15-
20°. The reaction mixture is stirred for an hour, treated with
saturated solution of ammonium chloride and extracted with
ether (3x50 ml). Ether extracts are washed with brine and
dried with sodium sulfate. The product is isolated by
distillation at reduced pressure. 2: colourless liquid: bp 79-
81° C (2 mm Hg); 2: 1H NMR (60 MHz, CCl4): δ = 0.33 – 0.5
(m, 2 H); 0.57 – 0.73 (m, 2 H); 1.37 (s, 3 H); 1.73 (s, 2 H); 3.47
– 3.60 (m, 1 H); 3.92 (s, 4 H).
(11) Brown, H. C.; Fletcher, R. S.; Johannesben, R. B. J. Am.
Chem. Soc. 1951, 73, 212.
(12) Compound 5 was prepared in moderate yield by the reaction
of cyclopropylidene phosphorane with 2-methyl-2-
(7) Vasilevsky, D. A.; Sviridov, S. V.; Kulinkovich, O. G. Zh.
Org. Khim. 1991, 27, 2132; J. Org. Chem. USSR 1991, 27,
1885.
formyldioxolane, followed by removal of acetal protection
and high activity of 5 in reactions of conjugated addition with
C-, O- nucleophiles and hydrogen chloride has been
demonstrated.13
(8) A solution of 13 mmol of compound 2 and 0.01 g of p-
toluenesulfonic acid in 20 ml of dichloromethane and 5 ml of
acetone is refluxed for 12 hours. 0.5 ml of acetone and 1 mg
of p-toluenesulfonic acid are added to the solution every 4
hours. The reaction mixture is washed with 5% solution of
sodium carbonate and brine, and then dried with calcium
chloride. The product is isolated by distillation at reduced
pressure. 3: colourless liquid: bp 92°C (20 mm Hg); 3:
1H NMR (60 MHz, CCl4): δ = 0.30 – 0.50 (m, 2 H); 0.60 –
0.80 (m, 2 H); 2.13 (s, 3 H); 2.53 (s, 2 H); 3.73 – 3.90 (m, 1 H).
(9) A solution of 10 mmol of compound 3 in 10 ml of pyridine is
cooled to -5°C. 20 mmol of p-toluenesulfonic chloride are
(13) Lechevallier, A.; Huet, F.; Conia, J. M. Tetrahedron 1983, 39,
3307. Lechevallier, A.; Huet, F.; Conia, J. M. Tetrahedron
1983, 39, 3317. Lechevallier, A.; Huet, F. Tetrahedron 1983,
39, 3329.
Article Identifier:
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Synlett 1999, No. 07, 1053–1054 ISSN 0936-5214 © Thieme Stuttgart · New York