4
Tetrahedron
ng MAN
All melting points were determined on a Y
A
an
C
aco
C
M
E
P
P
m
T
e
E
lti
D
U
U
sin
S
g
C
P
R
roc
I
e
P
d
T
ure 2; Yield: 10% (183 mg), Colorless crystal;
point (mp) apparatus and are uncorrected. Infrared spectra were
recorded with a JASCO FT/IR 4100 spectrophotometer. H, C,
MP 166.2–166.7 °C; IR (KBr): 2916, 2885, 2861, 1459, 1389,
1
13
-1 1
758, 689, 527 cm ; H NMR (400 MHz, CDCl ) δ 2.68 (s, 3H),
3
2 13
31
and P NMR spectral data were obtained with JEOL JNM-ECS
00 instruments. Chemical shifts are quoted in ppm using
3.21 (d, J = 11.6 Hz, 2H), 7.37–7.51 (m, 4H); C NMR (100
HP
1 2
4
MHz, CDCl ) δ 23.3, 44.2 (d, J = 53.4 Hz), 70.6 (d, J = 9.5
3 CP CP
1
tetramethylsilane (δ = 0 ppm) as the reference for H NMR
spectroscopy, CDCl (δ = 77.0 ppm) for C NMR spectroscopy,
and 85% H PO (δ = 0 ppm) for P NMR spectroscopy. Mass
Hz), 125.2, 127.8, 131.4, 135.9, 138.6, The ipso carbon peak was
not observed.; P NMR (160 MHz, CDCl ) δ 56.6, 60.3; HRMS-
ESI (m/z): [M + H] calcd for C H P S : 466.7761, found:
13
31
3
3
31
+
3
4
9
10 3 8
spectra were measured with a JEOL JMS-T100LP spectrometer.
Elemental analysis was performed with a YANACO CHN-
CODER JM-10 model analyzer. Column chromatography was
carried out on silica gel (spherical, neutral, 40–50 µm, Kanto
Chemical Co., Japan).
466.7747; Anal Cacld for C H P S : C, 23.17; H, 1.94. Found: C,
9 9 3 8
23.02; H, 2.09.
.1.6.
4
7-(3-Methoxyphenyl)-2,4,6,8,9-pentathia-1,3,5-
triphosphaadamantane 1,3,5-trisulfide (2f).
Using Procedure 2; Yield: 39% (419 mg), Colorless crystal;
MP 181.1–181.7 °C; IR (KBr): 2922, 2869, 2830, 1460, 785,
4
.1.1. General Procedure 1: Synthesis of 2 (recrystallization
alone):
-1
1
2
6
91, 533 cm ; H NMR (400 MHz, CDCl ) δ 3.12 (d, J = 10.8
3 HP
Hz, 2H), 3.87 (s, 3H), 7.08 (dd, J = 8.2, 2.2 Hz, 1H), 7.14 (dd, J
2.2, 2.2 Hz, 1H), 7.20 (dd, J = 8.2, 2.2 Hz, 1H), 7.49 (dd, J =
A mixture of acetophenone derivative 1 (0.860 mmol) and
=
P4S10 (8.60 mmol) in benzene (5 mL) was stirred under refluxing
temperature for 20 h. After cooling to room temperature, the
reaction mixture was filtered through an 11G-4 glass filter and
13
1
8
5
.2, 8.2 Hz, 1H); C NMR (100 MHz, CDCl ) δ 42.9 (d, J
=
3
CP
3.4 Hz), 55.9, 111.7, 117.0, 117,1, 131.7, 141.8, 161.2, The
31
quaternary carbon peak was not observed.; P NMR (160 MHz,
CDCl ) δ 56.7, 62.0; HRMS-ESI (m/z): [M + H] calcd for
washed with CHCl (80 mL). The filtrate was evaporated at 40
3
+
°
C, and then the residue was purified by recrystallization from
3
C H OP S : 482.7710, found: 482.7728; Anal Cacld for
hexane/CHCl to give 2 as a solid.
9
10
3 8
3
C H OP S : C, 22.40; H, 1.88. Found: C, 22.27; H, 1.99.
9
9
3 8
4
.1.2. General Procedure 2: Synthesis of 2 (short silica gel
column chromatography followed by recrystallization):
4
.1.7.
7-(m-Tolyl)-2,4,6,8,9-pentathia-1,3,5-
triphosphaadamantane 1,3,5-trisulfide (2g).
A mixture of acetophenone derivative 1 (2.25 mmol) and
P4S10 (22.5 mmol) in benzene (12 mL) was stirred under
refluxing temperature for 20 h. After cooling to room
temperature, the reaction mixture was filtered through an 11G-4
Using Procedure 2; Yield: 46% (480 mg), Colorless crystal;
MP 168.6–168.7 °C; IR (KBr): 2915, 2865, 1459, 1389, 780,
-1
1
6
92, 533 cm ; H NMR (400 MHz, CDCl ) δ 2.45 (s, 3H), 3.13
3
2 13
(d, J = 10.8 Hz, 2H), 7.36–7.49 (m, 4H); C NMR (100 MHz,
HP
1
glass filter and washed with CHCl (80 mL). The filtrate was
3
CDCl ) δ 21.8, 42.8 (d, J = 54.4 Hz), 122.4, 126.1, 130.5,
3
CP
evaporated at 40 °C, and then the residue was filtered through a
1
32.8, 141.0, The ipso carbon peak and the quaternary carbon
silica gel column chromatography (CHCl ). The eluate was
31
3
peak were not observed.; P NMR (160 MHz, CDCl ) δ 56.8,
6
3
evaporated at 40 °C, and then the residue was purified by
+
2.2; HRMS-ESI (m/z): [M + H] calcd for C H P S : 466.7761,
9 10 3 8
recrystallization from hexane/CHCl to give 2 as a solid.
3
found: 466.7762; Anal Cacld for C H P S : C, 23.17; H, 1.94.
9
9 3 8
Found: C, 23.21; H, 1.98.
4
1
.1.3. 7-Phenyl-2,4,6,8,9-pentathia-1,3,5-triphosphaadamantane
,3,5-trisulfide (2a).
4
.1.8. 7-(3-Bromophenyl)-2,4,6,8,9-pentathia-1,3,5-
triphosphaadamantane 1,3,5-trisulfide (2h).
Using Procedure 1; Yield: 46% (179 mg), Colorless crystal;
MP 184.2–184.7 °C; IR (KBr): 2920, 2873, 1459, 758, 710, 687,
Using Procedure 2; Yield: 29% (356 mg), Colorless crystal;
MP 181.8–182.5 °C; IR (KBr): 2918, 2871, 1470, 1077, 795,
689, 564, 536 cm-1; 1H NMR (400 MHz, CDCl3) δ 3.10 (d,
2JHP = 10.8 Hz, 2H), 7.47 (dd, J = 8.0, 8.0 Hz, 1H), 7.59 (d, J =
8.4 Hz, 1H), 7.71 (d, J = 8.4 Hz, 1H), 7.76–7.78 (m, 1H); 13C
NMR (100 MHz, CDCl3) δ 42.6 (d, 1JCP = 54.4 Hz), 69.5 (d,
2JCP = 7.6 Hz), 124.2, 124.7, 128.7, 132.0, 135.1, 142.4; 31P
NMR (160 MHz, CDCl3) δ 55.7, 60.9; HRMS-ESI (m/z): [M +
H]+ calcd for C8H779BrP3S8: 530.6710, found: 530.6731; Anal
Cacld for C8H6BrP3S8: C, 18.08; H, 1.14. Found: C, 17.96; H,
-
1
1
2
5
2
32 cm ; H NMR (400 MHz, CDCl ) δ 3.14 (d, J = 11.2 Hz,
3 HP
13
H), 7.57–7.61 (m, 3H), 7.62–7.67 (m, 2H); C NMR (100
1
2
MHz, CDCl ) δ 42.8 (d, J = 53.4 Hz), 70.3 (d, J = 8.6 Hz),
1
CDCl ) δ 56.7, 62.0; HRMS-ESI (m/z): [M + H] calcd for
3
CP
CP
31
25.6, 130.7 (×2), 132.0 (×2), 140.5; P NMR (160 MHz,
+
3
C H P S : 452.7605, found: 452.7593; Anal Cacld for C H P S :
8
8
3
8
8
7 3 8
C, 21.23; H, 1.56. Found: C, 21.09; H, 1.77.
4
.1.4. 7-(2-Methoxyphenyl)-2,4,6,8,9-pentathia-1,3,5-
triphosphaadamantane 1,3,5-trisulfide (2b).
1
.28.
Using Procedure 2; Yield: 14% (146 mg), Colorless crystal;
MP 180.2–180.8 °C; IR (KBr): 2935, 2914, 2833, 1459, 756,
4
.1.9.
7-(3-Nitrophenyl)-2,4,6,8,9-pentathia-1,3,5-
triphosphaadamantane 1,3,5-trisulfide (2i).
-
1
1
2
6
87, 532 cm ; H NMR (400 MHz, CDCl ) δ 3.39 (d, J = 10.0
3 HP
Hz, 2H), 3.94 (s, 3H), 7.10 (d, J = 8.0 Hz, 1H), 7.14 (dd, J = 8.0,
Using Procedure 2; Yield: 10% (137 mg), Pale yellow crystal;
MP 196.0–196.8 °C; IR (KBr): 2926, 2868, 1523, 1459, 1348,
8
1
5
1
.0 Hz, 1H), 7.54 (dd, J = 8.0, 8.0 Hz, 1H), 7.64 (d, J = 8.0 Hz,
1
3
1
-1
1
2
H); C NMR (100 MHz, CDCl ) δ 42.5 (d, J = 50.6 Hz),
778, 696, 533 cm ; H NMR (400 MHz, CDCl
3
) δ 3.18 (d, JHP
=
3
CP
2
6.3, 70.1 (d, J = 8.6 Hz), 114.0, 122.0, 126.62, 126.64, 133.0,
57.7; P NMR (160 MHz, CDCl ) δ 56.3, 63.1; HRMS-ESI
11.2 Hz, 2H), 7.84 (dd, J = 8.0, 8.0 Hz, 1H), 8.03 (dd, J = 8.0,
2.0 Hz, 1H), 8.46 (dd, J = 8.0, 2.0 Hz, 1H), 8.51 (dd, J = 2.0, 2.0
CP
31
3
+
13
1
(m/z): [M + H] calcd for C H OP S : 482.7710, found:
Hz, 1H);2 C NMR (100 MHz, CDCl
3
) δ 42.6 (d, JCP = 54.3 Hz),
9
10
3 8
4
82.7699; Anal Cacld for C H OP S : C, 22.40; H, 1.88. Found:
69.5 (d, JCP = 7.6 Hz), 120.9, 126.6, 131.8, 132.0, 142.5, 149.3;
P NMR (160 MHz, CDCl
H] calcd for C H NO P S : 497.7455, found: 497.7478; Anal
9
9
3 8
31
C, 22.66; H, 2.12.
3
) δ 54.8, 60.1; HRMS-ESI (m/z): [M
+
+
8
7
2 3 8
4
.1.5.
7-(o-Tolyl)-2,4,6,8,9-pentathia-1,3,5-
Cacld for C H NO P S : C, 19.31; H, 1.22; N, 2.81. Found: C,
8
6
2 3 8
triphosphaadamantane 1,3,5-trisulfide (2c).
1
9.24; H, 1.39; N, 2.89.