530
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 3, March, 2007
L. A. Krinitskaya
1
~
0 mmol) in acetone (20 mL), the mixture was stirred for 6 h at
20 °С and left in refrigerator for 14 h. Then the mixture was
was cooled down, NaHCO (0.5 g, 6 mmol) was added, and the
resulting mixture was extracted with ether. The ether extract was
3
concentrated to dryness and suspended in ether (20 mL). The
dried with anhydrous MgSO , after which ether was evapoꢀ
4
precipitate of NEt •HBr was filtered off, washed with ether on
rated in vacuo. Compound 9 was obtained (0.32 g, ~100%),
3
2
0
the filter, the combined ether extract was concentrated to dryꢀ
ness. After crystallization from hexane compound 5 was obꢀ
tained (1.47 g, 64%), m.p. 88—89 °С. Found (%): С, 46.95;
nD 1.4420. Found (%): С, 70.33; Н, 9.77; N, 9.46. C H NO.
9 15
1
Calculated (%): C, 70.55; H, 9.87; N, 9.14. H NMR (80 МHz,
3
CDCl ), δ: 1.14 (d, 2×3 Н, СН(СН ) , J = 7.0 Hz); 1.31 (s,
3
3 2
Н, 6.23; N, 5.82. C H14BrNO. Calculated (%): C, 47.11;
6 Н, 5,5ꢀMe ); 2.23 (s, 2 Н, СH —CO); 2.82 (sept, 1 Н,
2 2
9
1
СН(СН3)2, 3J = 7.0 Hz). IR (CCl ), ν/cm : 1660 (C=N);
–1
H, 6.08; N, 6.04. H NMR (400 МHz, C D ), δ: 0.90, 0.92,
6
6
4
1
.09, 1.52 (all s, 3 Н each, 2,2,6,6ꢀMe ); 2.20 (s, 1 Н, СH); 4.25
1750 (С=O).
4
–
1
(
s, 1 Н, CHBr). IR (CCl ), ν/cm : 1765 (С=0).
B. Compound 2 (10.7 g, 70 mmol) was placed into a distillaꢀ
tion apparatus and heated up to 175 °С, then the temperature
was gradually raised up to 205 °С. During heating the product
was distilled, which by its refractive index and chromatographic
behaviour was identical with the product of rearrangement of
compound 2 in the presence of oxalic acid.
4
3
ꢀBenzylideneꢀ2,2,6,6ꢀtetramethylꢀ1ꢀazabicyclo[3.1.0]ꢀ
hexanꢀ4ꢀone (6). Potassium hydroxide (0.3 g, 5 mmol) was added
to a solution of compound 2 (0.92 g, 6 mmol) and freshly disꢀ
tilled benzaldehyde (0.64 g, 6 mmol) in EtOH (10 mL). The
reaction mixture was stirred for 3 days at ~20 °С, then the
solvent was removed in vacuo, ether (10 mL) was added, КОН
was filtered off, and filtrate was concentrated in vacuo. Comꢀ
pound 6 (0.83 g, 57.4%) was obtained, m.p. 88.5—89.5 °С.
Found (%): С, 79.56; Н, 8.07; N, 6.11. C H NO. Calcuꢀ
lated (%): C, 79.66; H, 7.93; N, 5.81. 1H NMR (60 МHz,
CDCl —CCl ), δ: 1.29, 1.38, 1.40, 1.51 (all s, 3 Н each,
,2,6,6ꢀMe ); 2.60 (s, СH); 7.34 (m, Ph); 7.38 (s, НС=).
4
IR (CCl ), ν/cm : 3074 (СН=); 1725 (С=0); 1630 (С=С).
3ꢀHydroxyiminoꢀ2ꢀisopropylꢀ5,5ꢀdimethylꢀ1ꢀpyrroline (10).
Potassium acetate (0.2 g) and hydroxylamine chlorohydrate
(0.14 g) were added to a solution of compound 9 (0.32 g) in
water (10 mL). The mixture was kept for 24 h. The formed
precipitate of oxime was filtered off and dried. Compound 10
(0.12 g, 32%) was obtained. The product can be sublimed at the
temperatures higher 100 °С without melting. Found (%):
С, 64.61; Н, 9.58; N, 16.38. C H N O. Calculated (%):
16
19
3
4
2
–
1
4
9
16
2
4
ꢀHydroxyꢀ2,2,6,6ꢀtetramethylꢀ1ꢀazabicyclo[3.1.0]hexane
C, 64.27; H, 9.52; N, 16.66.
(
7). Sodium borohydride (0.08 g, 2.1 mmol) was added to a
2,2,6,6ꢀTetramethylpiperidinꢀ3,4ꢀdione (11). A suspension
of compound 5 (0.16 g, 0.7 mmol) in water (5 mL) was cooled
down with iceꢀcold water and 48% aq. HClO4 (0.2 mL) was
added to it. The mixture was stirred for 6 h, kept at ~20 °C for
solution of compound 2 (0.31 g, 2 mmol) in EtOН (5 mL)
at 0 °С, which was stirred for 1 h. Then the mixture was kept at
~
20 °С for 15 h, the solvent was removed in vacuo, and the
product was extracted from the solid residue with benzene. Benꢀ
zene extract was concentrated in vacuo and the residue was
crystallized from hexane. Compound 7 was obtained (0.31 g,
~14 h, neutralized with NaHCO (0.2 g), and the product was
3
extracted with ether. The extract was dried with MgSO , conꢀ
4
centrated in vacuo, and the residue was sublimed in vacuo. Prodꢀ
~
100%), m.p. 121—122 °С. Found (%): С, 69.44; Н, 10.86;
uct was obtained (0.071 g, 61%) by all characteristics identical
with compound 11 synthesized by Rassat method.
1
2
N, 9.12. C H NO. Calculated (%): C, 69.65; H, 11.04; N, 9.03.
9
17
1
H NMR (360 МHz, C D ), δ: 1.05, 1.10, 1.12, 1.48 (all s,
4ꢀBenzylideneꢀ2ꢀ(2ꢀhydroxypropꢀ2ꢀyl)ꢀ5,5ꢀdimethylꢀ3ꢀpyrꢀ
rolidinone (12). Water (2 mL) and 48% aq. HClO4 (0.5 mL)
were added to a cooled with iceꢀcold water solution of benzylꢀ
ideneketone 6 (0.18 g, 0.75 mmol) in EtOH (5 mL). The mixꢀ
ture was kept at ~20 °C for 24 h, after which EtOH was evapoꢀ
6
6
3
Н each, 2,2,6,6ꢀMe ); 1.52, 1.83 (both dd, 1 Н each, 2 CH ,
4 2
2
3
3
J = 13.8 Hz, J = 7.8 Hz); 2.12 (d, 1 Н, CH, J = 6.3 Hz); 4.65
3
(
ddd, CHOH, J = 6.3 Hz).
2
ꢀ(2ꢀHydroxypropꢀ2ꢀyl)ꢀ5,5ꢀdimethylꢀ3ꢀpyrrolidinone (8).
Perchloric acid (aq. 48%, 1.4 mL) was added dropwise to a
solution of compound 2 (0.61 g, 4 mmol) in water (5 mL)
at 20 °С, during which the precipitate of perchlorate of comꢀ
pound 2 was formed. The reaction mixture was kept at 20 °С for
rated in vacuo. Water (5 mL) and NaHCO (0.25 g) were added
to a stirred residue. The product was extracted with ether, the
3
extract was dried with MgSO , ether was evaporated in vacuo,
4
the residue was washed with hexane, and the hexane solution
was discarded. After washing with hexane the solid product was
remained. After recrystallization from hexane compound 12 was
obtained (0.091 g, 50%), m.p. 85 °С. Found (%): С, 78.91;
Н, 8.50; N, 5.38. C H NO. Calculated (%): C, 79.01; H, 8.64;
2
4 h, during which the precipitate was gradually dissolving. The
solution was neutralized with NH OH (1 mL), extracted with
4
ether, and the extract was dried with anhydrous MgSO . The
4
drying agent was filtered off and filtrate was concentrated
in vacuo. Compound 8 was obtained (0.64 g, 94%) as colorless
crystals, m.p. 62.5—63 °С (after crystallization from hexane and
sublimation in vacuo). Found (%): С, 63.20; Н, 9.88; N, 8.06.
C H NO . Calculated (%): C, 63.14; H, 10.01; N, 8.18.
1
6
21
1
N, 5.76. H NMR (60 МHz, CDCl —CCl ), δ: 1.23, 1.53
3
4
(both s, 3 Н each, 5,5ꢀMe ); 1.31 (s, 6 Н, Me COH); 3.50 (s,
2
2
1 Н, СH—N); 7.38 (s, 5 Н, Ph); 7.50 (s, 1 Н, СН=).
9
17
2
1
H NMR (80 МHz, CDCl ), δ: 1.17, 1.21 (both s, 3 Н each,
References
3
5
2
,5ꢀMe ); 1.24, 1.36 (both s, 3 Н each, СMe ); 2.20 (s,
2 2
1
Н, СH —С=О); 3.29 (s, 1 Н, СН—N). H NMR
1. O. L. Lebedev and S. N. Kazarnovskii, Trudy po khimii i
khimicheskoy tekhnologii [Chemistry and Chemical Technolꢀ
ogy Transactions], Gor´kii State University Publ., Gor´kii,
1959, p. 649.
2. M. B. Neiman, E. G. Rozantsev, and Yu. G. Mamedova,
Nature, 1963, 200, 256.
2
(
CDCl —CF COOH), δ: 1.43 (s, 3 Н, Me); 1.46 (s, 6 Н,
3 3
5
,5ꢀMe ); 1.75 (s, 3 Н, Me); 2.61 (s, 2 Н, СH —С=О); 3.88
2 2
–
1
(
(
br.s, 1 Н, СН—N). IR (CCl ), ν/cm : 3270 (NН); 1730
С=O); 3430 (OH).
4
2
ꢀIsopropylꢀ5,5ꢀdimethylꢀ1ꢀpyrrolinꢀ3ꢀone (9). А. A solution
of compound 2 (0.31 g, 2 mmol) and oxalic acid (0.32 g,
.5 mmol) in water (5 mL) was refluxed for 5 h. The solution
3. E. G. Rozantsev and L. A. Krinitskaya, Tetrahedron, 1965,
21, 491.
2