1156
M. C. Davis, J. E. P. Dahl, and R. M. K. Carlson
1,3-Adamantanedicarbonyl Dichloride (5)
A 100-mL round-bottomed flask equipped with magnetic stirbar was charged
with 50 mL of SOCl followed by 4 g of 4 (18 mmol). A condenser was
2
attached that was equipped with an aqueous NaOH gas scrubber. The
mixture was stirred and refluxed for 6 h. The excess SOCl was distilled
2
under reduced pressure, leaving a pale yellow solid (4.52 g, 97%). The solid
was slurried with hexanes and filtered on a medium frit to give the title
[14]
compound as an off-white, crystalline solid. Mp 83–86 8C (lit.
90 8C).
d (CDCl ): 2.35 (pent, J ¼ 2.5 Hz, 2H), 2.24 (s, 2H), 2.01 (q, J ¼ 14.0 Hz,
H
3
8
H), 1.75 (t, J ¼ 2.9 Hz, 2H); d (CDCl ): 178.82, 51.44, 40.14, 38.07,
C
3
3
4.84, 27.95.
1,3-Diisocyanatoadamantane (1)
A 100-mL round-bottomed flask equipped with magnetic stirbar was charged
with 5 and 1,2-dichloroethane. The mixture was cooled in an ice bath, and a
previously prepared solution of NaN in H O was added in one portion. The
3
2
mixture was vigorously stirred, and the cooling bath was removed. After 1 h,
1
H NMR of an aliqout of the organic phase showed complete formation of
,3-adamantanedicarbonyl diazide (6) [dH (CDCl ): 2.19 (pent, J ¼ 3.1 Hz,
1
3
2
H), 1.95 (s, 2H), 1.82 (q, J ¼ 11.1 Hz, 8H), 1.68 (t, J ¼ 2.8 Hz, 2H); d
C
(CDCl ): 184.39, 43.16, 39.41, 37.77, 35.18, 27.87]. The organic layer was
3
separated and washed once with 5% NaHCO and then brine. The organic
3
layer was dried over anhydrous MgSO and transferred to a 100-mL round-
4
bottomed flask equipped with magnetic stirbar. The solution was refluxed, and
1
after 1 h H NMR showed complete consumption of 6. The solution was
rotary evaporated (10 torr, rt) leaving the title compound as a colorless liquid
that was more than 98% pure by NMR and GCMS. The compound could be
recrystallized from hexanes at 220 8C. d (CDCl ): 2.26 (pent, J ¼ 2.8 Hz,
H
3
2
H), 1.98 (s, 2H), 1.82 (d, J ¼ 2.8 Hz, 8H), 1.56 (t, J ¼ 2.8 Hz, 2H); d
C
(CDCl ): 123.43, 56.25, 52.14, 43.89, 34.17, 30.39. Elemental analysis calcu-
lated for C H N O : C, 66.04; H, 6.47; N, 12.84. Found: C, 65.68; H, 6.63;
3
1
2
14
2
2
þ†
N, 13.71. EI-MS: M (%): 218 (41); 176 (44); 161 (100); 120 (39).
1,6-Diisocyanatodiamantane (2)
A 100-mL round-bottomed flask was charged with 25 mL of anhydrous
CH Cl and 1.38 g of triphosgene (4.9 mmol, 1 equiv). The solution was
cooled in an ice bath while a solution of 1.07 g of 7 (4.9 mmol) and 1.97 g
2
2
of TEA (19.5 mmol, 4 equiv) in 5 mL of CH Cl was added dropwise over
2
2
10 min. Copious solids precipitated during this time. After the addition, the
cooling bath was removed, and the mixture was stirred at rt for 2 h. The