(2.764, sh). 1H NMR: d 1.72 (m, 34 H), 3.56 (m, 4 H), 3.84 (m,
4 H), 4.28 (d, 4 H, 2J \ 15.7), 4.34 (d, 4 H, 2J \ 15.7), 4.84 (t, 4
H, 3J \ 2.95 Hz). 13C NMR: d 18.5 ([), 23.8 ([), 25.0 ([),
29.8 ([), 43.2 ([), 53.8 ([), 61.4 ([), 62.6 (C ), 78.7 (C ),
72.6 (C ), 86.2 (C ), 97.1(C ), 120.2 (]), 127.6(]), 127.9
quat
quat
quat
(]), 128.3(]), 138.0 (C ). MS (CI, positive ion, NH ): m/z
quat
3
(442.56): calc. C
(%) 460 (100) [M ] NH `]. C
H
O
4
32 26
2
86.85, H 5.92; found C 86.86, H 6.02%.
quat
quat
86.1 (C ), 96.3 (]). MS (CI, negative ion, NH ): m/z (%) 669
quat
3
(4) [M [ 1], 568 (6) [M [ OTHP], 101 (100) [OTHP].
1,11-Bis(tetrahydropyran-2-yloxy)-4,8-bis[3-(tetrahydro-
pyran-2-yloxy)prop-1-ynyl]undeca-2,9-diyne-4,8-diol 11b.
To a solution of THP-protected propargyl alcohol (8.94 g,
63.8 mmol) in 60 ml of THF at [30 ¡C was added 42.5 ml of
butyllithium (64 mmol, 1.5 M in hexane). The solution was
stirred for 0.5 h, 1,5-pentanedioic acid diethyl ester 10b (2.0 g,
10.6 mmol) added, the reaction mixture allowed to warm to
0 ¡C and stirred 0.5 h at this temperature. Work up following
Dibenzyl ether of 11a, i.e. 12a. To a suspension of NaH (390
mg, 16 mmol) in 100 mL of THF at room temperature was
slowly added a solution of 11a (5.0 g, 7.5 mmol) in 20 mL of
THF. The mixture was stirred for 0.5 h, benzyl bromide (2.0
ml, 16.4 mmol) and n-Bu NI (1.4 g, 3.7 mmol) were added and
4
stirring was continued for 5 h. The reaction mixture was
poured into aqueous NH Cl, the aqueous phase extracted
4
the procedure described for 11a and CC (PE : Et O, 1 : 1)
with ether (4 ] 80 ml), the combined organic phases were
2
gave 5.5 g (79%) of 11b (R \ 0.46, Et O), as a colorless oil. IR
washed with brine (20 mL), dried over Na SO and the
f
2
2
4
(Ðlm): l \ 3385, 2925, 1156 cm~1. UV (CH CN): j
(log
solvent removed in vacuo. CC of the crude product
3
max
e) \ 192 (3.689), 196 (3.577, sh), 212 (2.894, sh), 258 nm (2.163).
1H NMR: d 1.72 (m, 32 H), 1.95 (s, 4 H), 3.53 (m, 4 H), 3.83
(m, 4 H), 4.28 (d, 4 H, 2J \ 15.7), 4.34 (d, 4H, 2J \ 15.7 Hz),
4.84 (m, 4 H). 13C NMR: d 18.5 ([), 19.3 ([), 25.0 ([), 29.8
([), 43.0 ([), 53.9 ([), 61.4 ([), 62.7 (C ), 78.9 (C ), 86.1
(PE : Et O, 9 : 1) gave 6.2 g (98%) of 12a (R \ 0.12), as a
2
f
yellow oil. IR (KBr): l \ 3031, 2942, 1121, 736 cm~1. UV
(CH CN): j
(log e) \ 194 (4.871), 210 (4.241), 218 (4.148),
3
max
228 nm (3.897). 1H NMR: d 1.68 (m, 28 H), 2.01 (m, 4 H), 3.53
(m, 4 H), 3.85 (m, 4 H), 4.33 (m, 8 H), 4.75 (s, 4 H), 4.81 (m, 4
H), 7.32 (m, 10 H). 13C NMR: d 19.0 ([), 25.3 ([), 26.9 ([),
quat
3
quat
(C ), 96.3 (]). MS (CI, negative ion, NH ): m/z (%) 656 (5)
quat
[M], 655 (10) [M [ 1], 554 (5) [M [ OTHP], 101 (60)
30.2 ([), 42.8 ([), 54.1 ([), 62.0 ([), 67.9 ([), 69.8 (C ),
quat
[OTHP]. C
8.48%.
H O : calc. C 67.66, H 7.98; found C 67.56, H
81.1 (C ), 84.0 (C ), 96.8 (]), 127.4 (]), 127.8 (]), 128.2
37 52 10
quat
quat
(]), 138.4 (C ). MS (CI, positive ion, NH ): m/z (%) 868 (2)
quat
3
[M ] NH `], 85 (100).
4
Dibenzyl ether of 11b, i.e. 12b. NaH (320 mg, 13 mmol), 11b
1,12-Dibromo-4,9-bis(benzyloxy)-4,9-bis(3-bromoprop-1-
(4.0 g, 6.1 mmol), n-Bu NI (1.1 g, 3.0 mmol) and benzyl
ynyl)dodeca-2,10-diyne 13a. To a solution of PPh (14.2 g, 54.2
4
bromide (1.6 ml, 13 mmol) were allowed to react in 20 ml
3
mmol) and Br (2.8 mL, 8.7 g, 54.2 mmol) in 150 ml of
2
THF according to the procedure given for compound 12a.
CH Cl were added at 0 ¡C 6.6 g (7.7 mmol) of 12a and the
Work up and CC (Et O) yielded 4.7 g (93%) of 12b (R \
2
2
reaction mixture was stirred for 15 h at room temperature.
100 ml of the solvent were distilled o†, the suspension was
treated with 100 ml PE, the precipitate collected by Ðltration
and washed with PE (2 ] 30 ml). The combined Ðltrate was
evaporated in vacuo and the residue chromatographed on
silica gel (PE : Et O, 1 : 1) to yield 4.5 g (77%) of 13a (R \
2
f
0.66), as a yellowish oil. IR (KBr): l \ 3031, 2941, 1120, 736
cm~1. UV (CH CN): j
(log e) \ 194 (4.873), 210 (4.307),
3
max
224 nm (3.563). 1H NMR: d 1.65 (m, 26 H), 2.02 (m, 4 H), 3.50
(m, 4 H), 3.83 (m, 4 H), 4.30 (d, 4 H, 2J \ 15.7), 4.35 (d, 4 H,
2J \ 15.7 Hz), 4.76 (s, 4 H), 4.81 (m, 4 H), 7,32 (m, 10 H). 13C
NMR: d 19.0 ([), 19.5 ([), 25.3 ([), 30.2 ([), 42.5 ([), 54.1
([), 61.9 ([), 67.9 ([), 69.8 (C ), 81.2 (C ), 83.9 (C ),
2
f
0.54), as colorless crystals, mp \ 74 ¡C. IR (KBr): l \ 3062,
2846 cm~1. UV (CH CN): j
(log e) \ 194 (4.906), 202
quat
quat
quat
96.8 (]), 127.3 (]), 127.7 (]), 128.2 (]), 138.4 (C ).
3
max
(4.576, sh), 212 (4.509, sh), 228 nm (3.950, sh). 1H NMR: d 1.66
(m, 4 H), 2.01 (m, 4 H), 3.94 (s, 8 H), 4.72 (s, 4 H), 7.33 (m, 10
H). 13C NMR: d 13.7 ([), 23.9 ([), 42.5 ([), 68.2 ([), 69.7
(C ), 80.5 (C ), 84.5 (C ), 127.6 (]), 127.9 (]), 128.3 (]),
quat
1,11-Dibromo-4,8-bis(benzyloxy)-4,8-bis(3-bromoprop-1-
ynyl)undeca-2,9-diyne 13b. Triphenylphosphine 22.0 g (84.0
quat
quat
quat
138.0 (C ). MS (CI, positive ion, NH ): m/z (%) 784 (100)
[M ] NH `], 108 (42) [OBn ] 1]. C
50.16, H 3.95; found C 50.17, H 3.96%.
mmol), Br 4.3 ml (13.4 g, 84.0 mmol) and 12b 10.0 g (12.0
quat
4
3
H
2
Br O : calc. C
mmol) were allowed to react in 200 ml of CH Cl at 0 ¡C
32 30
4 2
2
2
according to the procedure described for compound 13a.
Work up and CC (PE : Et O, 1 : 1) yielded 9.6 g (80%) of 13b
2
1,8-Di(benzyloxy)bicyclo[6.6.4]octadeca-4,11-diene-2,6,
9,13-tetrayne 14a. To a solution of HMDS (2.88 ml, 13.8
mmol) in 10 ml of THF was added butyllithium (9.3 ml, 13.8
mmol) at 0 ¡C. The mixture was stirred at room temperature
for 10 min, HMPA (24.0 ml, 138.0 mmol) added and this solu-
tion was added via syringe pump over 5 h to a solution of 13a
(1.7 g, 2.22 mmol) in 80 ml of THF at [45 ¡C. The reaction
mixture was poured into 200 ml of ice cold aqueous sat.
(R \ 0.7), as a yellow oil. IR (Ðlm): l \ 3004, 2926, 1606, 737
f
cm~1. UV (CH CN): j
(log e) \ 192 (4.868), 210 (4.492, sh),
3
max
248 (3.760, sh), 412 nm (2.952). 1H NMR: d 2.03 (m, 6 H), 3.95
(s, 8 H), 4.74 (s, 4 H), 7.32 (m, 10 H). 13C NMR: d 13.8 ([),
19.4 ([), 42.1 ([), 68.2 ([), 69.7 (C ), 80.7 (C ), 84.3
quat
quat
(C ), 127.6 (]), 127.9 (]), 128.3 (]), 138.0 (C ). MS (CI,
quat
quat
4
positive ion, NH ): m/z (%) 770 (74) [M ] NH `], 664 (78)
3
[M ] 1 [ OBn], 108 (63) [OBn ] 1].
NH Cl, the aqueous phase extracted with ether (4 ] 40 ml),
4
the combined organic phases were washed subsequently with
ice cold aqueous 1% HCl (20 ml), water (20 ml), aqueous sat.
NaHCO solution (20 ml) and brine (20 ml). The organic
1,8-Di(benzyloxy)bicyclo[6.6.3]heptadeca-4,11-diene-2,6,
9,13-tetrayne 14b. A solution of HMDS (1.3 ml, 6.0 mmol),
butyllithium (4.0 ml, 6.0 mmol) and HMPA (10.4 ml, 60.0
mmol) in 6 ml of THF was added dropwise over 5 h to a
solution of 13b (752 mg, 1.0 mmol) in 80 ml of THF at
[45 ¡C. The reaction mixture was worked up as described for
3
phase was dried over Na SO , the solvent removed in vacuo
2
4
at room temperature and the residue Ðltered over a short
silica gel column with ether. The ether solution was again con-
centrated in vacuo and the crude product puriÐed by CC
(PE : Et O, 9 : 1). Yield: 130 mg (14%) of 14a (R \ 0.21), as
compound 14a and CC (PE : Et O, 9 : 1) gave 30 mg (7%) of
2
f
2
colorless crystals, mp \ 190 ¡C (decomp.). IR (KBr): l \ 3426,
14b (R \ 0.32), as colorless crystals. 1H NMR: d 1.14 (m, 6
f
3046, 2924, 1454 cm~1. UV (CH CN): j
(log e) \ 194
H), 4.64 (s, 4 H), 5.84 (s, 4 H), 7.29 (m, 10 H). 13C NMR: d
3
max
(4.816), 214 (4.269, sh), 260 (4.324), 272 nm (3.979, sh). 1H
NMR: d 2.10 (m, 4 H), 2.65 (m, 4 H), 4.76 (s, 4 H), 5.88 (s, 4
H), 7.34 (m, 10 H). 13C NMR: d 24.6 ([), 39.7 ([), 68.3 ([),
29.7 ([), 31.9 ([), 68.6 ([), 72.3 (C ), 86.2 (C ), 97.1
quat
quat
(C ), 121.4 (]), 127.6 (]), 128.0 (]), 128.3 (]), 138.0 (C ).
quat
quat
MS (EI): m/z (%) 428 (1) [M`], 91 (100) [CH Ph].
2
New J. Chem., 2001, 25, 912È916
915