ACCEPTED MANUSCRIPT
13
(
m, 2H, Ar-H), 6.50 – 6.39 (m, 2H, Ar-H), 3.85 (s, 2H, SeCH
CDCl3) 146.68, 138.65, 137.03, 131.32, 130.48, 120.33, 116.48, 115.63, 32.51; MS (ESI): m/z = found
63.85 [M +1]; calcd. 263.02 [M ]; HRMS calcd. for C H NSe [M +1]: 264.02860, found 264.02748
2 2
), 3.62 (s, 2H, NH ); C NMR (100 MHz,
δ
+
+
+
2
[
1
3
13
+
M +1].
4
4
3
-((2,2-Diethoxyethyl)selanyl)aniline (4c)
-((2,2-Diethoxyethyl)selanyl)aniline was synthesized from 4-(2-(4-aminophenyl)diselanyl)benzenamine
(170 mg, 0.5 mmol), 2-bromo-1,1-diethoxyethane (166 l, 1.1 mmol), Starks’ catalyst (22.5 mg, 2.5%
µ
mol) and NaBH (57 mg, 1.5 mmol). The product formation was followed by TLC petroleum ether:
4
EtOAc= 12:2, R = 0.39, purified by column silica gel chromatography with petroleum ether: EtOAc=
f
1
6
:1.5. Colorless oil; Yield: 257 mg (89%). H NMR (300 MHz, CDCl
3
)
δ
7.42 – 7.34 (d, J = 7.37 HZ, 2H,
), 3.03
146.17, 135.90,
Ar-H), 6.62 – 6.55 (d, J = 6.58, 2H, Ar-H), 4.66 (t, J = 5.7 Hz, 1H, CH), 3.67 – 3.46 (m, 4H, 2CH
2
1
3
(
d, J = 5.7 Hz, 2H, SeCH ), 1.19 (t, J = 7.1 Hz, 6H, 2CH ); C NMR (75 MHz, CDCl )
δ
2
3
3
+
+
1
17.11, 115.70, 102.30, 61.70, 32.23, 15.23; MS (ESI): m/z = found 312.04 [M +Na]; calcd. 289.06 [M ];
+
+
HRMS calcd. for C H NO Se [M +Na]: 312.0498, found 312.04597 [M +Na].
12
19
2
2
2
-((4-Aminophenyl)selanyl)-3-methylnaphthalene-1,4-dione (5)
-((4-Aminophenyl)selanyl)-3-methylnaphthalene-1,4-dione was
synthesized
from
4-(2-(4-
aminophenyl)diselanyl)benzenamine 3 (170 mg, 0.5 mmol), 2-methyl-3-bromo-l,4-naphthoquinone (275
mg, 1.1 mmol), Starks’ catalyst (Aliquat 336) (22.5 mg, 2.5% mol) and NaBH (57 mg, 1.5 mmol). The
4
product formation was followed by TLC petroleum ether: EtOAc= 8:3, R = 0.32, purified by column
f
silica gel chromatography with petroleum ether: EtOAc= 3:1. Brown solid; Yield: 305.50 mg (89%); mp
o
1
1
2
62-164 C. H NMR (300 MHz, DMSO)
δ
7.97 (ddt, J = 11.8, 6.9, 3.4 Hz, 2H, Ar-H), 7.87 – 7.77 (m,
), 1.98 (s, 3H, CH );
δ 181.84, 181.73, 149.10, 147.31, 147.24, 135.69, 134.08, 133.77, 131.69,
H, Ar-H), 7.28 – 7.19 (m, 2H, Ar-H), 6.55 – 6.44 (m, 2H, Ar-H), 5.39 (s, 2H, NH
C NMR (75 MHz, CDCl3)
31.65, 126.34, 126.27, 114.65, 111.92, 16.50; MS (ESI): m/z = found 344.95 [M +1], 366.20 [M +Na];
2
3
1
3
+
+
1
+
+
+
calcd. 343.01 [M ]; HRMS calcd. for C H NO Se [M +Na]: 366.00037, found 365.99930 [M +Na].
1
7
13
2
2
,3-bis((4-Aminophenyl)selanyl)naphthalene-1,4-dione (6)
Compound 6 was prepared from compound 3 (344 mg, 1 mmol), 2,3-dichloronaphthalene-1,4-dione (226
mg, 1 mmol), Starks’ catalyst (45 mg, 5% mol) and sodium tetrahydridoborate (189.15 mg, 5 mmol). The
progress of the product formation was followed by TLC petroleum ether: EtOAc= 4:1.5, R = 0.28,
f
purified by column silica gel chromatography with petroleum ether: EtOAc= 3:1. Brown solid; Yield:
1
6
10.50 mg (78%). H NMR (400 MHz, DMSO)
δ
7.96 (m, 3H, Ar-H), 7.84 (m, 3H, Ar-H), 7.29 (m, 3H,
1
3
Ar-H), 6.52 (m, 3H, Ar-H), 3.36 (s, 4H, 2NH
2
). C NMR (100 MHz, DMSO) δ 180.06, 175.00, 149.62,
1
48.64, 142.37, 136.48, 134.23, 131.90, 131.10, 126.82, 114.47, 111.04. MS (ESI): m/z = found 522.40
+
+
[
M +Na]; calcd. 499.95 [M ].
3
-((4-Aminophenyl)selanyl)propanenitrile (7a)
Compound 7a was prepared from compound 3 (340 mg, 1 mmol), 3-chloropropanenitrile (197 mg, 2.2
mmol), and sodium borohydride (113.49 mg, 3 mmol) in EtOH (15 ml). The progress of the product
formation was followed by TLC petroleum ether: EtOAc= 4:1, R
f
= 0.32. White powder; Yield: 357 mg
1
(
79%). H NMR (400 MHz, DMSO)
δ 7.26 – 7.22 (m, 2H, Ar-H), 6.56 – 6.52 (m, 2H, Ar-H), 5.29 (s, 2H,
1
3
NH ), 2.88 (t, J = 7.49 Hz, 2H, CH ), 2.75 – 2.70 (t, J = 6.84 Hz, 2H, CH ). C NMR (100 MHz, DMSO)
2
2
2
+
δ
149.06, 136.09, 134.21, 119.77, 114.74, 110.94, 22.60, 18.17. MS (ESI): m/z = found 248.60 [M +Na];
+
+
+
9 10 2
calcd. 226.09 [M ]; HRMS calcd. for C H N Se [M +Na]: 226.0009, found 248.9901 [M +Na].
Methyl 3-((4-aminophenyl)selanyl)propanoate (7b)
Compound 7b was prepared from compound 3 (340 mg, 1 mmol), methyl 3-chloropropanoate (269 µl, 2.2
mmol), and sodium borohydride (113.49 mg, 3 mmol) in EtOH (15 ml). The progress of the product
formation was followed by TLC petroleum ether: EtOAc= 4:1, R = 0.31. Yellow oil; Yield: 404 mg
f
1
(
5
78%). H NMR (400 MHz, DMSO)
δ
7.21 (d, J = 8.4 Hz, 2H, Ar-H), 6.53 (d, J = 8.4 Hz, 2H, Ar-H),
), 2.86 (t, J = 7.1 Hz, 2H, CH ), 2.62 (t, J = 7.2 Hz, 2H, CH ). C
2 2
13
.24 (s, 2H, NH
2
), 3.58 (s, 3H, CH
3
NMR (100 MHz, DMSO)
δ
172.11, 148.78, 135.95, 114.69, 111.95, 51.37, 34.57, 22.71. MS (ESI): m/z =
+
+
+
found 282.10 [M +Na]; calcd. 259.01 [M ]; HRMS calcd. for C H NO Se [M +Na]: 259.0112, found
1
0
13
2
+
2
60.0184 [M +1].
1
7