Biology Reference
In-Depth Information
9.5.2
Synthesis of 1,8-Bis[
Trans
-(Ethynyl)Pd(PEt
3
)
2
(NO
3
)]
Anthracene (3)
Both 1,8-diethynylanthracene (400.5 mg, 1.77 mmol) and
trans
-
Pd(PEt
(1817.3 mg, 4.39 mmol) were added to a 100 mL
round-bottom Schlenk flask under N
)
Cl
3
2
2
atmosphere. Then, 75 mL of
2
dried and degassed Et
NH was syringed into the flask. After 10 min
stirring, CuCl (40 mg, ~6.6 mol.%) was added. Immediately, greenish
yellow gelatinous fluorescent precipitate appeared and on stirring it
turned into a yellow solution. After 48 h stirring, the solvent was
removed under vacuum to yield a brown solid. The crude solid
was separated by column chromatography using silica gel (60-
120 mesh) with first toluene-
2
-hexane (80:20 v/v) and then with
ethylacetate. The fraction eluted with ethylacetate was concentrated
to minimum volume and
n
-hexane was added. On triturating yielded
deep yellow powder as pure
n
2
in 70% isolated yield. Anal. calcd. for
1
C
H
Pd
Cl
P
: C 51.44, H 6.99. Found: C 51.51, H 7.08.
H NMR
42
68
2
2
4
(400 MHz; CDCl
/ppm = 9.39 (s, 1 H), 8.36 (s, 1 H), 7.8 (d, 2 H),
7.48 (d, 2 H), 7.36-7.32 (m, 2 H), 2.07-2.00 (m, 24 H), 1.33-1.15 (m,
36 H).
):
δ
3
31
1
13
1
P{
H}
NMR (CDCl
, 121.4 MHz)
δ
/ppm: 17.79 (s).
C{
H}
3
(CDCl
) 132.44 (C
, anthracene), 131.72 (C
, anthracene), 129.89
3
10
9
(C
, anthracene), 127.47 (C
, anthracene), 126.82 (C
, anthracene),
1
11
12
126.19 (C
, anthracene), 125.59 (C
, anthracene), 125.03 (C
,
2
4
3
anthracene), 106.24 (C
, ethynyl), 102.71 (C
, ethynyl), 20.45 (CH
,
¢
¢
2
1
2
∫
-1
Et), 9.11 (CH
, Et). IR (KBr):
ν
(C
C) = 2101 cm
. UV-vis (CHCl
)
3
3
-1
-1
l
): 214 (16434), 263 (16512), 361 (6290), 385
(6774), 405 (8590), 428 (8330), 883 (1568), 906 (1448).
Degassed methanolic solution (15 mL) of silver nitrate (273.1
mg, 1.6 mmol) was added to a stirred solution of
/nm(
e
/cm
M
max
2
(525.3 mg, 0.54
under nitrogen atmosphere.
The reaction mixture was stirred under nitrogen atmosphere at
room temperature for 24 h in absence of light and filtered through
the Celite-545, washed with CHCl
mmol) in 30 mL of degassed CHCl
3
. The filtrate and washings were
concentrated ~3 mL and cold diethyl ether was added to precipitate
out
3
1
3
as brown solid in a 60% isolated yield.
H NMR (400 MHz;
CDCl
/ppm = 9.24 (s, 1 H), 8.37 (s, 1 H), 7.84 (d, 2 H), 7.48 (d,
2 H), 7.38-7.34 (m, 2 H), 1.95-1.85 (m, 24 H), 1.34-0.98 (m, 36 H).
31
):
δ
3
P{
1
H}
NMR (CDCl
, 121.4 MHz): 19.17 (s). ESI-MS:
m
/
z
= 970.32
3
+
[2 - NO
]
.
3
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