Crisscross-Overlapped Tetrathiafulvalenophanes
J . Org. Chem., Vol. 62, No. 16, 1997 5573
1
3
.30 (m, 8H), 3.31-3.38 (m, 8H). Anal. Calcd for C14
C, 17.73; H, 1.70. Found: C, 17.80; H, 1.69.
,3,6,7-Tet r a k is[(3-iod op r op yl)t h io]-1,4,5,8-t et r a t h i-
H
16
S
8
I
4
:
of 16d as orange needles. Mp 201 °C dec; H NMR (CS
2
/CDCl
3
)
δ 1.56-1.62 (m, 8H), 1.67-1.76 (m, 16H), 2.77 (t, J ) 6.8 Hz,
-
1
2
8H), and 2.90 (t, J ) 6.8 Hz, 8H); IR (KBr) 1065 cm . Anal.
a fu lva len e (11b). Reaction of 10b (4.02 g, 6.29 mmol) with
NaI (37.8 g, 252 mmol) in acetone (230 mL) and dioxane (80
mL) for 1 day gave, after recrystallization from acetone, 4.80
Calcd for C32
4.04.
40
H S18: C, 38.37; H, 4.02. Found: C, 38.13; H,
Gen er a l P r oced u r e for Oxid a tion of 16. Syn th esis of
Bis[2′-oxo-1′,3′-dith iole-4′,5′-diylbis(eth ylen edith io)]-1,4,5,8-
tetr a th ia fu lva len e (17a ). To a suspension of crude 16a (130
mg) in CHCl (20 mL) was added a solution of Hg(OAc) (100
3 2
mg, 0.31 mmol) in AcOH (3 mL). The mixture was stirred at
room temperature for 12 h and then concentrated to give a
1
g (76%) of 11b as orange needles. Mp 74-75 °C; H NMR
3
(CDCl ) δ 2.12 (quintet, J ) 6.6 Hz, 8H), 2.95 (t, J ) 6.6 Hz,
8
3
2
H), 3.33 (t, J ) 6.6 Hz, 8H); 13C NMR (CDCl
3
) δ 4.2, 32.8,
: C, 21.52; H,
6.7, 110.7, 128.0. Anal. Calcd for C18
.40. Found: C, 21.77; H, 2.40.
H
24
I
4
S
8
2
,3,6,7-Tetr a k is[(4-iod obu tyl)th io]-1,4,5,8-tetr a th ia fu l-
va len e (11c). Reaction of 10c (2.78 g, 4.01 mmol) with NaI
12.0 g, 80.1 mmol) in acetone (150 mL) and dioxane (50 mL)
for 1 day gave, after recrystallization from acetone, 3.44 g
white solid. The solid was extracted with CS
the extract was successively washed with H
O (2 × 50 mL)
and saturated aqueous NaHCO
solution (2 × 50 mL) and
dried over MgSO Column chromatography on silica gel
eluted with 2:1 CH /CS gave a pale yellow solid, which was
2
(50 mL), and
2
(
3
4
.
(
(
81%) of 11c as orange needles. Mp 79-80 °C; 1H NMR
CDCl ) δ 1.76 (quintet, J ) 6.8 Hz, 8H), 1.96 (quintet, J )
.8 Hz, 8H), 2.84 (t, J ) 6.8 Hz, 8H), 3.20 (t, J ) 6.8 Hz, 8H);
2
Cl
2
2
3
further purified by preparative GPC to give 50 mg (18% based
1
6
on 11a ) of 17a as a pale yellow powder. Mp 254 °C dec; H
1
3
C NMR (CDCl
Calcd for C22
.04.
,3,6,7-Tetr akis[(5-iodopen tyl)th io]-1,4,5,8-tetr ath iafu l-
va len e (11d ). Reaction of 10d (10.0 g, 13.3 mmol) with NaI
24.0 g, 160 mmol) in acetone (200 mL) and dioxane (50 mL)
for 1 day gave, after recrystallization from acetone, 12.2 g
3
) δ 5.8, 30.4, 31.9, 35.1, 110.6, 127.8. Anal.
2 3
NMR (CS /CDCl ) δ 2.87 (ddd, J ) 5.0, 9.7, 13.9 Hz, 4H), 3.11
H
32
I
4
S
8
: C, 24.91 H, 3.04. Found: C, 25.15; H,
(ddd, J ) 6.1, 9.7, 11.6 Hz, 4H), 3.20 (ddd, J ) 5.0, 9.6, 11.6
Hz, 4H), 3.44 (ddd, J ) 6.1, 9.6, 13.9 Hz, 4H); IR (KBr) 1667
3
-
1
+
2
16 2
cm ; MS m/ z 800 (M ). Anal. Calcd for C20H O S16: C,
29.98; H, 2.01. Found: C, 29.76; H, 1.94.
2,7:3,6-Bis[2′-oxo-1′,3′-d ith iole-4′,5′-d iylbis(p r op a n e-1,3-
d iyld ith io)]-1,4,5,8-tetr a th ia fu lva len e (17b). Reaction of
(
(
(
82%) of 11d as orange needles. Mp 57-58 °C; 1H NMR
CDCl ) δ 1.54 (quintet, J ) 6.7 Hz, 8H), 1.67 (quintet, J )
.7 Hz, 8H), 1.86 (quintet, J ) 6.7 Hz, 8H), 2.83, (t, J ) 6.7
crude 16b (601 mg) with Hg(OAc)
CHCl (20 mL) and AcOH (3 mL) for 12 h gave, after
recrystallization from CS /hexane, 360 mg (28% based on 11b)
of 17b as yellow plates. Mp 234 °C dec; H NMR (CS
δ 1.96 (quintet, J ) 6.9 Hz, 8H), 2.97 (t, J ) 6.9 Hz, 8H), 2.98
(t, J ) 6.9 Hz, 8H); 13C NMR (CS
/CDCl ) δ 29.5, 34.7, 34.9,
118.7, 127.1, 127.4, 189.4; IR (KBr) 1669 cm . Anal. Calcd
for C24 16: C, 33.62; H, 2.82. Found: C, 33.58; H, 2.83.
2
(431 mg, 1.35 mmol) in
3
3
6
2
1
3
1
Hz, 8H), 3.20 (t, J ) 6.7 Hz, 8H); C NMR (CDCl
3
) δ 6.5, 28.7,
2.9, 35.9, 39.3, 110.3, 127.7. Anal. Calcd for C26 : C,
7.97; H, 3.61. Found: C, 27.99; H, 3.61.
Gen er a l P r oced u r e for Cou p lin g of 7 a n d 11. Syn th e-
2 3
/CDCl )
3
2
40 4 8
H I S
2
3
-
1
sis of 2,7:3,6-Bis[2′-th ioxo-1′,3′-d ith iole-4′,5′-d iylbis(eth -
ylen ed ith io)]-1,4,5,8-tetr a th ia fu lva len e (16a ). Two THF
solutions (50 mL each) of the zincate 7 (310 mg, 0.34 mmol)
and of 11a (320 mg, 0.34 mmol) were added simultaneously
into refluxing THF (100 mL) over a period of 8 h, and the
mixture was further refluxed for 2 days. Evaporation of the
solvent gave a reddish black tar, which was washed with
acetone (200 mL) to afford a yellow solid (130 mg) containing
24 2
H O S
2,7:3,6-Bis[2′-oxo-1′,3′-d ith iole-4′,5′-d iylbis(bu ta n e-1,4-
d iyld ith io)]-1,4,5,8-tetr a th ia fu lva len e (17c). Reaction of
crude 16c (412 mg) with Hg(OAc)
CHCl (30 mL) and AcOH (5 mL) for 12 h gave, after
recrystallization from CS /hexane, 128 mg (14% based on 11c)
of 17c as yellow plates. Mp 207-208 °C dec; H NMR (CS
CDCl ) δ 1.77 (quintet, J ) 7.0 Hz, 8H), 1.86 (quintet, J ) 7.0
Hz, 8H), 2.84 (t, J ) 7.0 Hz, 8H,), 2.90 (t, J ) 7.0 Hz, 8H);
NMR (CS /CDCl ) δ 28.2, 29.1, 35.0, 36.5, 114.0, 126.9, 128.1,
2
(277 mg, 0.87 mmol) in
3
2
1
2
/
3
1
3
1
6a . Because of the poor solubility of 16a , the crude solid was
used for the conversion to 17a without further purification.
An analytical sample was obtained by silica gel column
C
2
3
-
1
189.4; IR (KBr) 1671 cm . Anal. Calcd for C28
36.81; H, 3.53. Found: C, 37.09; H, 3.53.
32 2
H O S16: C,
chromatography with 2:1 CH
tallization from CS as yellow needles. Mp 270 °C dec; H
NMR (CS /CDCl ) δ 2.88 (ddd, J ) 5.0, 9.7, 13.9 Hz, 4H), 3.14
ddd, J ) 6.1, 9.7, 11.6 Hz, 4H), 3.23 (ddd, J ) 5.0, 9.6, 11.6
2 2 2
Cl /CS and subsequent recrys-
1
2
2,7:3,6-Bis[2′-oxo-1′,3′-d ith iole-4′,5′-d iylbis(p en ta n e-1,5-
d iyld ith io)]-1,4,5,8-tetr a th ia fu lva len e (17d ). Reaction of
2
3
(
crude 16d (706 mg) with Hg(OAc)
CHCl (70 mL) and AcOH (14 mL) for 12 h gave, after
recrystallization from CHCl /MeOH, 428 mg (13% based on
11d ) of 17d as orange plates. Mp 130-131 °C; H NMR (CS
CDCl ) δ 1.57-1.63 (m, 8H), 1.67-1.73 (m, 16H), 2.81 (t, J )
6.8 Hz, 8H), 2.88 (t, J ) 6.8 Hz, 8H); C NMR (CS
27.1, 28.6, 29.5, 35.6, 36.5, 112.6, 126.8, 127.3, 189.8; IR (KBr)
2
(450 mg, 2.37 mmol) in
Hz, 4H), 3.42 (ddd, J ) 6.1, 9.6, 13.9 Hz, 4H); IR (KBr) 1076
3
-
1
cm . Anal. Calcd for C20
C, 28.52; H, 1.93.
H
16
S
18: C, 28.82; H, 1.93. Found:
3
1
2
/
2
,7:3,6-Bis[2′-th ioxo-1′,3′-d ith iole-4′,5′-d iylbis(p r op a n e-
3
1
3
1
,3-d iyld ith io)]-1,4,5,8-tetr a th ia fu lva len e (16b). Reaction
2 3
/CDCl ) δ
of the zincate 7 (1.55 g, 1.64 mmol) and 11b (1.50 g, 1.49 mmol)
in THF (750 mL) for 36 h gave 601 mg of crude 16b as a yellow
solid. Silica gel chromatography and recrystallization from
-
1
1669 cm . Anal. Calcd for C32
Found: C, 39.46; H, 4.15.
40 2
H O S16: C, 39.64; H, 4.16.
CS
2
/hexane afforded an analytical pure sample of 16b as
Gen er a l P r oced u r e for In tr a m olecu la r Cou p lin g of 17.
Syn th esis of Eth ylen ed ith io-Br id ged Tetr a th ia fu lva le-
n op h a n e (6a ). Triethyl phosphite (0.72 mL, 4.2 mmol) was
slowly added to a refluxing solution of 17a (168 mg, 0.21 mmol)
in toluene (50 mL), and the mixture was refluxed for additional
37 h. Evaporation of the solvent provided an orange solid,
which was purified with silica gel column chromatography
1
yellow plates. Mp 231-232 °C dec; H NMR (CS
2
/CDCl
3
) δ
2
.01 (quintet, J ) 6.9 Hz, 8H), 3.02 (t, J ) 6.9 Hz, 8H), 3.03
-
1
(
C
t, J ) 6.9 Hz, 8H); IR (KBr) 1062 cm
.
Anal. Calcd for
18: C, 32.40; H, 2.72. Found: C, 32.39; H, 2.66.
,7:3,6-Bis[2′-th ioxo-1′,3′-d ith iole-4′,5′-d iylbis(bu ta n e-
,4-d iyld ith io)]-1,4,5,8-tetr a th ia fu lva len e (16c). Reaction
24 24
H S
2
1
of the zincate 7 (1.89 g, 2.00 mmol) and 11c (1.06 g, 1.00 mmol)
in THF (400 mL) for 12 h gave 412 mg of crude 16c as an
orange solid. Silica gel chromatography and recrystallization
using CS
2 2
as an eluent and then recrystallized from CS /
hexane to give 123 mg (76%) of 6a as yellow needles. Mp 290
1
°C dec; H NMR (CS
2
/CDCl
3
) δ 2.75-2.85 (m, 8H), 3.08-3.17
3
from CS
2
/hexane afforded an analytical pure sample of 16c
(m, 8H); 13C NMR (CS
2
/CDCl ) δ 53.5, 122.9, 130.0; MS (DI)
1
+
as yellow plates. Mp 199 °C dec; H NMR (CS
2
/CDCl
3
) δ 1.77-
m/ z 768 (M ); UV-vis (THF) λ (log ꢀ) 258 (4.46), 333 (4.47)
nm. Anal. Calcd for C20
31.01; H, 2.05.
1
8
.89 (m, 16H), 2.80 (t, J ) 6.8 Hz, 8H), 2.92 (t, J ) 6.8 Hz,
16
H S16: C, 31.22; H, 2.10. Found: C,
-1
H); IR (KBr) 1062 cm . Anal. Calcd for C28
32
H S18: C, 34.82;
H, 4.25. Found: C, 34.63; H, 4.25.
,7:3,6-Bis[2′-th ioxo-1′,3′-d ith iole-4′,5′-d iylbis(p en ta n e-
,5-d iyld ith io)]-1,4,5,8-tetr a th ia fu lva len e (16d ). Reaction
P r op a n e-1,3-d iyld it h io-Br id ged Tet r a t h ia fu lva len o-
p h a n e (6b). Reaction of 17b (228 mg, 0.26 mmol) with
triethyl phosphite (13.3 mL, 76.1 mmol) in toluene (100 mL)
2
1
of the zincate 7 (3.17 g, 3.36 mmol) and 11d (2.50 g, 2.24 mmol)
in THF (500 mL) for 36 h gave 706 mg of crude 16d as a
reddish black solid. Silica gel chromatography and recrystal-
for 24 h gave, after recrystallization from CS
(65%) of 6b as orange crystals. Mp 278 °C dec; H NMR (CS
2
/hexane, 139 mg
1
2
/
1
3
CDCl
3
) δ 2.11-2.20 (m, 8H), 2.75-2.80 (m, 16H); C NMR
+
lization from CHCl
3
/MeOH afforded an analytical pure sample
(CS /CDCl ) δ 32.7, 34.2, 112.9, 125.0; MS (DI) m/ z 824 (M );
2
3