1
96ꢀꢁꢁꢁꢂꢀL.J. Silverberg et al.: Solvolytic reactions of the N-tosylaziridines of (+)-2-carene and (+)-3-carene
δ 170.5, 143.1, 140.5, 133.8, 129.6, 128.2, 127.2, 84.2, 56.6, 43.7, 36.2, 27.2, the crude material was chromatographed on flash silica gel, elut-
2
3.5, 23.1, 22.6, 21.7, 21.5; IR: 3268 (br), 2970, 1724, 1429, 1386, 1368, 1321, ing with a gradient of ethyl acetate/hexanes (5%, 15%, 30%, 50%
-1
1
254, 1215, 1156, 1132, 1091, 1018, 815, 735, 661, 576 cm . HRMS. Calcd for ethyl acetate) to yield 9 (30.8 mg, 25%) as a solid. Unreacted 8 (22.9
+
[
C H NO SNa] , m/z 388.1558. Found: m/z 388.1556.
mg, 22%) was also recovered. Compound 9: R (30% ethyl acetate/
19
27
4
f
1
hexanes): 0.35; H NMR: δ 7.77 (d, J ꢀ= ꢀ 8.2 Hz, 2H), 7.28 (d, J ꢀ= ꢀ 8.2 Hz,
N-[(1R,4R)-4-(2-hydroxypropan-2-yl)-1-methylcyclohex-2-en-1- 2H), 4.76 (d, J ꢀ= ꢀ 8.3 Hz, 1H), 3.54 (q, J ꢀ= ꢀ 8.3 Hz, 1H), 2.48 (m, 1H), 2.41
yl]-4-methylbenzenesulfonamide (6)ꢀAziridine 4 (50.1 mg) was (s, 3H), 1.92 (s, 3H), 1.73 (m, 1H), 1.40 (s, 6H), 0.95 (s, 3H), 0.91–1.00
1
3
weighed directly into a 5 mL round-bottom flask and treated with dis- (m, 2H), 0.78 (t, J ꢀ= ꢀ 4.6 Hz, 1H), 0.23 (t, J ꢀ= ꢀ 6.4 Hz, 1H); C NMR:
tilled water (2.0 mL). The heterogeneous mixture was stirred at 80°C δ 170.6, 143.4, 138.1, 129.7, 127.2, 83.8, 59.6, 46.5, 30.0, 25.2, 24.1, 24.0,
for 17 h, then cooled, poured into a separatory funnel, treated with 23.7, 22.6, 21.7, 18.7, 10.1; IR: 3269 (br), 2925, 1727, 1446, 1258, 1157, 1081,
-1
+
saturated sodium chloride, and extracted three times with ethyl ace- 1018, 911, 814, 714, 663 cm . HRMS. Calcd for [C H NO SNa] m/z
1
9
27
4
tate. The organic solutions were combined, washed with water and 388.1558. Found: m/z 388.1552.
then saturated sodium chloride, dried over sodium sulfate, filtered,
and concentrated to an oil/solid. Chromatography on flash silica gel,
Preparationof N-[(1R,3S,4S,6S)-4-hydroxy-4,7,7-trimethylbicyclo-
4.1.0]hept-3-yl]-4-methylbenzenesulfonamide (10) at room
temperatureꢀAziridine 8 (0.105 g) was weighed directly into a
0 mL pear-shaped flask. A stir bar and distilled water (4 mL) were
eluting with a gradient of ethyl acetate/hexanes (20%, 50%, 100%
ethyl acetate) yielded 6 (27.9 mg, 53%) as a solid. The solid was crys-
tallized from a mixture of ethyl acetate and hexanes to yield 12.2 mg
[
1
(
44% recovery); mp 142°C sharp; R (60% ethyl acetate/hexanes):
f
added. The heterogeneous mixture was stirred at room temperature
for 21 days, then poured into a separatory funnel, and extracted
three times with dichloromethane. The organic solutions were com-
bined and washed with saturated sodium chloride. The solution
was dried over sodium sulfate, filtered, and concentrated to an oil.
The crude material was chromatographed on flash silica gel, elut-
ing with a gradient of ethyl acetate/hexanes (5%, 30%, 50%, 100%
ethyl acetate) to yield 10 (11.2 mg, 12%) as an oil that solidified on
standing for 1 day. Unreacted 8 (24.2 mg, 23%) was also recovered.
1
0
.42; H NMR: δ 7.80 (d, J ꢀ= ꢀ 8.3 Hz, 2H), 7.30 (d, J ꢀ= ꢀ 8.3 Hz, 2H), 5.71
(
d, J ꢀ= ꢀ 10.4 Hz, 1H), 5.61 (dd, J ꢀ= ꢀ 10.4 Hz and 2.4 Hz, 1H), 4.51 (s, 1H),
.41 (s, 3H), 2.07 (m, 1H), 1.64 (m, 2H), 1.84 (m, 1H), 1.76 (m, 1H), 1.72
2
1
3
(
s, 1H), 1.57 (m, 1H), 1.34 (s, 3H), 1.17 (s, 3H), 1.12 (s, 3H); C NMR:
δ 143.1, 140.5, 134.0, 129.6, 128.9, 127.2, 72.7, 56.6, 46.3, 36.4, 28.0, 27.3,
2
6.2, 21.9, 21.7. IR: 3500 (br), 3272 (br), 2971, 1456, 1369, 1319, 1156,
-1
-
1
092, 815, 664, 556 cm . HRMS. Calcd for [C H NO S] , m/z 322.1477.
17 24 3
Found: m/z 322.1489.
Compound 10: mp 125–128°C; R (30% ethyl acetate/hexanes): 0.13;
f
N - [ ( 1 R, 4 R ) - 4 - ( 2- ( 2- hyd r ox ye t h ox y ) p r o p a n -2- y l ) -1-
methylcyclohex-2-en-1-yl]-4-methylbenzenesulfonamide (7)ꢀA
1
H NMR: δ 7.76 (d, J ꢀ= ꢀ 8.1 Hz, 2H), 7.28 (d, J ꢀ= ꢀ 8.1 Hz, 2H), 4.54 (d, J ꢀ= ꢀ
8
(
.5 Hz, 1H), 3.60 (q, J ꢀ= ꢀ 8.5 Hz, 1H), 2.41 (s, 3H), 2.08 (m, 1H), 1.72
1
0 mL round-bottom flask was oven-dried, fitted with septa, and
m, 1H), 1.6 (bs, 1H), 1.19 (s, 3H), 1.10 (s, 3H), 1.08 (s, 3H), 0.96–1.02
cooled under N . Aziridine 4 (53.8 mg) was weighed directly into
13
2
(m, 2H), 0.78 (t, J ꢀ= ꢀ 4.5 Hz, 1H), 0.22 (m, 1H); C NMR: δ 143.3, 138.2,
29.7, 127.2, 72.3, 59.8, 47.7, 29.9, 29.0, 27.6, 25.2, 23.4, 21.7, 18.8, 9.5; IR:
the flask. A stir bar, a condenser, a two-neck adaptor, and a tem-
perature probe were added. Ethylene glycol (2.14 mL) was added.
The heterogeneous mixture was stirred and warmed to 100°C with
a heating mantle. The mixture was stirred at 100°C for 18 h. The yel-
low solution was allowed to cool and then poured into a separatory
funnel. Saturated sodium chloride was added and the mixture was
extracted three times with ethyl acetate. The organic solutions were
combined and washed with saturated sodium chloride. The solution
was dried over sodium sulfate, filtered, and concentrated to an oil.
This was chromatographed on flash silica gel, eluting with a gradi-
ent of ethyl acetate/hexanes (20%, 40%, 60%, 100% ethyl acetate)
to yield 8 (24.8 mg, 38%) as a solid. The solid was crystallized from a
mixture of ethyl acetate and hexanes to yield white crystals (11.5 mg,
1
3
450 (br), 3272 (br), 2967, 1446, 1303, 1155, 1080, 1017, 917, 814, 734,
63 cm . HRMS. Calcd for [C H NO SNa] , m/z 346.1453. Found: m/z
-1
+
6
17
25
3
3
46.1454.
Preparation of 10 at 80°CꢀAziridine 8 (0.100 g) was weighed
directly into a 10 mL round-bottom flask and treated with distilled
water (4 mL). The heterogeneous mixture was stirred at 80°C for 17
h, then cooled, poured into a separatory funnel, and extracted three
times with ethyl acetate. The organic solutions were combined,
washed with saturated sodium chloride, dried over sodium sulfate,
filtered, and concentrated to an oil. The crude material was chroma-
tographed on flash silica gel, eluting with a gradient of ethyl acetate/
hexanes (5%, 30%, 50%, 100% ethyl acetate) to yield 10 (15.8 mg,
4
6% recovery); mp 137–138°C. R (60% ethyl acetate/hexanes): 0.49;
f
1
H NMR: δ 7.78 (d, J ꢀ= ꢀ 8.3 Hz, 2H), 7.29 (d, J ꢀ= ꢀ 10 Hz, 2H), 5.64 (d, J ꢀ= ꢀ
0 Hz, 1H), 5.54 (dd, J ꢀ= ꢀ 10 Hz and 2.5 Hz, 1H), 4.46 (s, 1H), 3.67 (s, 2H),
1
5%) as an oil that solidified on standing for 1 day. Also separated
1
was p-toluenesulfonamide (17.7 mg, 37%).
3
.42 (t, J ꢀ= ꢀ 4.8 Hz, 2H), 2.43 (s, 3H), 2.24 (m, 1H), 1.84 (m, 2H), 1.67 (m,
H), 1.56 (s, 1H), 1.35 (m, 1H), 1.27 (s, 3H), 1.09 (s, 3H), 1.06 (s, 3H);
C NMR: δ 140.8, 133.6, 129.9, 129.5, 127.5, 77.7, 62.7, 62.3, 57.0, 43.9, 36.9,
1
13
Acknowledgments: L.J.S. gratefully thanks Prof. Dou-
glass F. Taber (University of Delaware) for the gift of 1,
the late Prof. Charles Russell (Muhlenberg College) for
his help with and use of his department’s instrumenta-
tion, Prof. Mark Maroncelli (Penn State University Park)
for providing equipment, Prof. Gong Chen (Penn State
University Park) for his group’s assistance with analyti-
cal work, Dr. Phillip Smith (Penn State University Park
2
7.6, 23.3, 22.9, 22.1, 22.0; IR: 3407 (br), 3186 (br), 2933, 1672, 1380, 1357,
-
1
-
1
178, 1052 963, 735 cm . HRMS. Calcd for [C H NO S] , m/z 366.1739.
19 28 4
Found: m/z 366.1739.
N-[(1R,3S,4S,6S)-4-acetoxy-4,7,7-trimethylbicyclo[4.1.0]hept-
3
-yl]-4-methylbenzenesulfonamide (9)ꢀA 10 mL pear-shaped
flask was oven-dried, fitted with septa, and cooled under N . Aziri-
2
dine 8 (0.1022 g) was weighed directly into the flask. A stir bar and
glacial acetic acid (4 mL) were added. The solution was stirred at
room temperature for 21 days. The solvent was removed in vacuo and Metabolomics Core Facility, grant NSF MRI 1126373) for
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