4
50
M.K.G.Mekhael et al. · 2H-Azirine-3-methyl(phenyl)amines
give 214 mg (81.5%) of 19.IR (KBr): ν = 3390m, ane/Et O 5:2), the two products were purified by
2
3
1
1
9
315m, 3240m, 3200m, 3160s, 3100s, 3040s, 2960s, means of HPLC (Nucleosil 100Ð7, hexane/ethyl
695s, 1680s, 1615s, 1505s, 1470s, 1430s, 1370m, acetate 10:3, 0.5 ml/min, 13 atm): 80 mg (37.0%)
355s, 1305s, 1260s, 1205s, 1120s, 1080s, 1030s, of 22 as colorless crystals, m.p. 61.8Ð62.1 ∞C.IR
Ð1
1
40w, 865w, 765s, 740m, 695m, 660s cm
.
H
(KBr): ν = 3055w, 2969m, 2929m, 2869w, 1711s,
NMR (D -DMSO): δ = 10.07 (s, NH), 9.77 (s, 1651s, 1606s, 1494s, 1472s, 1460s, 1428m, 1385s,
6
NH), 7.51 (d-like, 1 arom.H), 7 4. 1 ( t-like, 1 arom. 1353s, 1306m, 1287m, 1248m, 1212s, 1158m, 1128s,
H), 7.30 (d-like, 1 arom.H), 7 2. 4( t-like, 1 arom. 1079m, 1045w, 1019m, 1000w, 947s, 856w, 802w,
1
3
Ð1 1
H), 3.49 (s, CH N), 1.52 (s, 2 CH ). C NMR (D6- 754s, 709w, 699w cm . H NMR (CDCl ): 7.25 (t-
3
3
3
DMSO): δ = 175.6 (s, N=C-NH ), 141.2, 136.5 (2s, like, 1 arom.H), 7 1. 5 ( d-like, 1 arom.H), 7 0. 3 ( t-
2
2
arom. C), 128.4, 124.8, 122.4, 110.7 (4d, 4 arom. like, 1 arom.H), 6 8. 1 ( d-like, 1 arom.H), 3 2. 0 ( s,
13
CH), 46.8 (s, C-3), 29.3 (q, CH N), 24.0 (q, 2 CH ). CH N), 2.29 (s, COCH ), 1.51 (s, 2 CH ).
C
3
3
3
3
3
+
CI-MS: m/z (%) = 175 (2, [M-BF ] ), 159 (4). NMR (CDCl ): 181.8 (s, N-C=O), 165.8 (s, N-C=
4
3
Analysis for C H BF N (262.05): calcd. C 50.42, N), 143.0, 136.9 (2s, 2 arom. C), 127.7, 122.1, 121.5,
11
15
4
2
H 5.77, N 10.69; found: C 50.35, H 5.76, N 10.76.
107.8 (4d, 4 arom.CH), 46 8. ( s, C-3), 28.3, 27.3
2q, COCH , CH N), 25.9 (q, 2 CH ).EI-MS: m/
(
3
3
3
+
.
2
(
-Amino-2,3-dihydro-1,3,3-trimethylindole hydrate z (%) = 216 (34, M ), 215 (31), 201 (57), 186 (25),
20)
175 (57), 160 (100).
As a minor compound, 40 mg (20.0%) of 2,3-
dihydro-1,3,3-trimethylindol-2-one (21) were ob-
tained as colorless crystals, m.p. 49.7 ∞C ([25]:
A solution of 19 (100 mg, 0.38 mmol) in the least
amount of water was cooled to 0 ∞C, and 10 ml of
aqueous NaOH (30%) were added.The mixture
was stirred for 20 min and extracted with CH Cl .
5
1
1
9
0 ∞C).IR (KBr): ν = 3060w, 2960m, 2920w, 2860w,
720s, 1615s, 1495s, 1470m, 1460m, 1380s, 1375m,
350s, 1310m, 1250m, 1125s, 1070m, 1045w, 1020w,
2
2
The organic phase was washed with brine and
dried over Na SO to give 67 mg (92%) of 20 as a
2
4
Ð1 1
40w, 760 m, 745m, 700m cm . H NMR (CDCl3):
yellow oil.IR (film): ν = 3300m, 3060w, 2970m,
δ = 7.16 (t-like, 1 arom.H), 7 1. 2 ( d-like, 1 arom.
H), 6.96 (t-like, 1 arom.H), 6 7. 5 ( d-like, 1 arom.
H), 3.12 (s, CH N), 1.30 (s, 2 CH ). C NMR
2
1
1
7
930m, 2870w, 1645s, 1610s, 1500s, 1470s, 1460 m,
390m, 1365m, 1310m, 1250w, 1220w, 1185w,
160w, 1120s, 1075m, 1020m, 1005m, 940m, 860w,
1
3
3
3
(
CDCl ): (see [34]).Analysis for C
H NO
11 13
Ð1
1
3
80w, 750s, 700m, 630m cm
.
H NMR (D6-
(
175.23): calcd. C 75.40, H 7.48, N 7.99; found:
DMSO): δ = 7.22Ð7.12, 6.89Ð6.79 (2m, 4 arom.
C 75.21, H 7.41, N 7.79.
1
3
H), 3.12 (s, CH N), 1.28 (s, 2 CH ). C NMR (D -
3
3
6
Hydrolysis of 20 and 22.A solution of 20
DMSO): δ = 174.7 (s, N=C-NH ), 144.6, 135.8 (2s,
2
(
100 mg, 0.52 mmol) in H O/THF (1:1 ν/ν, 15 ml
2
2
arom. C), 127.5, 121.8, 119.9, 106.5 (4d, 4 arom.
each) was refluxed for 3 days and extracted with
CH), 43.6 (s, C-3), 26.5 (q, CH N), 26.2 (q, 2 CH ).
3
3
Et O.The organic phase was washed with brine
and dried over Na SO to give 86 mg (94%) of 21.
1
2
H NMR (CDCl ): δ = 7.17 (t-like, 1 arom.H),
3
2
4
7
6
.08 (d-like, 1 arom.H), 6 8. 8 ( t-like, 1 arom.H),
A solution of 22 (50 mg, 0.23 mmol) in 10% HCl
.66 (d-like, 1 arom.H), 3 1. 9 ( s, CH N), 1.29 (s, 2
3
(
5 ml) was refluxed for 1 h and extracted with
13
CH3). C NMR (CDCl ): δ = 177.0 (s, N=C-NH ),
3
2
Et O.The organic phase was washed with aqueous
2
1
1
44.4, 135.8 (2s, 2 arom. C), 127.7, 121.9, 120.7,
06.8 (4d, 4 arom.CH), 44.6 (s, C-3), 27.1 (q,
NaHCO solution, brine, and dried over Na SO
to give 37 mg (91%) of 21.
3
2
4
CH N), 26.6 (q, 2 CH ).CI-MS: m/z (%) = 176
3
3
X-Ray crystal-structure determination of 19 and
2 (see Figs 1 and 2, Table 2) [35].
+
+
(
12), 175 (100, [M-NH ] or [M-OH] ).Analysis
3
2
for C H N O (192.26): calcd. C 68.72, H 8.39, N
1
1
16
2
All measurements were made on a Rigaku
1
4.57; found C 68.40, H 8.29, N 14.18.
AFC5R diffractometer using graphite-monochro-
˚
mated MoÐKα radiation (λ 0.71069A) and a 12
N-(2,3-Dihydro-1,3,3-trimethylindol-2-yliden)-
acetamide (22)
kW rotating anode generator.The data collection
and refinement parameters are given in Table 2,
To a solution of 19 (300 mg, 1.14 mmol) in pyri- and views of the molecules are shown in Figs 1
dine (3 ml), acetic anhydride (Ac O, 3 ml) was and 2.The intensities were corrected for Lorentz
2
added and the mixture was stirred at ca.23 ∞C for and polarization effects and, in the case of 19, an
1
6 h.Then, the solvent was evaporated and the
empirical absorption correction based on azi-
residue dissolved in CHCl , washed with H O and muthal scans of several reflections [36] was ap-
3
2
brine, and dried over Na SO .After filtration,
evaporation and column chromatography (hex- using SIR 92 [37] for 19 and SHELXS 97 [38] for
plied.Each structure was solved by direct methods
2
4
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