European Journal of Organic Chemistry
10.1002/ejoc.201601600
FULL PAPER
1
3
1
30.2 (2CH), 128.3 (CH), 125.8 (2CH), 121.9 (CH), 121.5 (Cq), 115.9
CH
(100.6 MHz, CDCl
131.2 (CH), 122.7 (CH), 120.3 (Cq), 114.6 (CH), 79.4 (Cq), 32.4 (CH
2
2
), 1.71 (s, 3H, CH
): δ = 193.7 (C=O), 157.9 (Cq), 157.3 (Cq), 138.2 (Cq),
),
) ppm; HRMS m/z (ESI) positive ion, calculated for
3 3
), 0.85 (t, J= 7.5 Hz, 3H, CH ) ppm; C NMR
(
CH), 35.3 (Cq), 31.1 (3CH ppm; HRMS m/z (ESI) positive ion,
3
)
3
+
calculated for C18
H
17KNO
2
: [M+K] 318.0896 Da; Found: 318.0898.
2
C
5.2 (CH
3
), 7.8 (CH
3
+
(
5-fluorobenzo[c]isoxazol-3-yl)(phenyl)methanone (4o): IR (KBr):
1
1
12
H
13ClNO
3
: [M+H] 254.0584; Found: 254.0585.
1
2
658, 1267, 809, 712 cm ; H NMR (400 MHz, CDCl
3
): δ = 8.32-8.28 (m,
1
1
-(2,1-benzisoxazol-3-yl)-3-hydroxypropan-1-one (4ch): IR (KBr):3433,
H), 7.80 (ddd, J= 9.6 Hz, J= 4.6 Hz, J= 0.8 Hz, 1H), 7.76 (ddd, J= 8.2
-
1 1
3
683, 1282, 1114, 753 cm ; H NMR (400 MHz, CDCl ): δ = 7.94 (dt, J=
8.8 Hz, J= 1.1 Hz, 1H), 7.65 (ddd, J= 9.1 Hz, J= 1.2 Hz, J= 0.9 Hz, 1H),
Hz, J= 2.3 Hz, J= 0.8 Hz, 1H), 7.71 (tt, J= 7.4 Hz, J= 1.3 Hz, 1H), 7.63-
1
3
7
.59 (m, 2H), 7.29 (ddd, J= 9.6 Hz, J= 8.5 Hz, J= 2.3 Hz, 1H) ppm;
C
7
6
2
1
1
.33 (ddd, J= 9.1 Hz, J= 6.5 Hz, J= 1.1 Hz, 1H), 7.20 (ddd, J= 8.8 Hz, J=
.5 Hz, J= 0.8 Hz, 1H), 4.06 (t, J= 5.5 Hz, 2H, CH ), 3.37 (t, J= 5.5 Hz,
), 2.51 (bs, 1H, OH) ppm; C NMR (100.6 MHz, CDCl ): δ =
89.6 (C=O), 159.4 (Cq), 157.6 (Cq), 131.4 (CH), 128.9 (CH), 121.0 (CH),
19.3 (Cq), 116.0 (CH), 57.4 (CH ), 42.4 (CH ) ppm; HRMS m/z (ESI)
KNO [M+K] 230.0220; Found:
3
NMR (100.6 MHz, CDCl ): δ = 181.2 (C=O), 161.8 (d, J= 253.6 Hz, C-F),
2
1
60.9 (d, J= 11.5 Hz, Cq), 155.4 (Cq), 135.8 (Cq), 133.9 (CH), 130.1
2CH), 128.8 (2CH), 124.8 (d, J= 31.7 Hz, CH), 121.8 (d, J= 12.6 Hz, Cq),
18.7 (d, J= 9.8 Hz, CH), 103.8 (d, J= 26.3 Hz, CH) ppm; HRMS m/z
1
3
H, CH
2
3
(
1
+
2
2
(
ESI) positive ion, calculated for C14
42.0610.
-(2,1-benzisoxazol-3-yl)-3-phenylprop-2-en-1-one (4ba): IR (KBr):
H
9
FNO
2
: [M+H] 242.0617; Found:
+
positive ion, calculated for
C
10
H
9
3
:
2
1
1
8
7
7
6
(
1
(
2
3
1
8
30.0223.
-(2,1-benzisoxazol-3-yl)-3-oxopropyl benzoate (4ci): IR (KBr): 1719,
-
1 1
658, 1597, 1155, 753 cm ; H NMR (400 MHz, CDCl
3
): δ = 8.17 (dt, J=
-1
1
683, 1282, 753, 707 cm ; H NMR (400 MHz, CDCl
3
): δ = 8.06 (dt, J=
.8 Hz, J= 1.1 Hz, 1H), 8.03 (d, J= 15.9 Hz, 1H), 7.82 (d, J= 15.9 Hz, 1H),
.77 (dd, J= 1.1 Hz, J= 0.8 Hz, 1H), 7.76-7.73 (m, 2H), 7.48-7.46 (m, 3H),
.43 (ddd, J= 9.1 Hz, J= 6.4 Hz, J= 1.0 Hz, 1H), 7.30 (ddd, J= 8.8 Hz, J=
.8 Hz, J= 1.1 Hz, 1H), 8.01-7.98 (m, 2H), 7.74 (ddd, J= 9.1 Hz, J= 1.2
Hz, J= 0.8 Hz, 1H), 7.54 (tt, J= 7.5 Hz, J= 1.7 Hz, 1H), 7.44-7.39 (m, 3H),
.29 (ddd, J= 8.8 Hz, J= 6.5 Hz, J= 0.8 Hz, 1H), 4.84 (t, J= 6.2 Hz, 2H,
7
1
3
.4 Hz, J= 0.8 Hz, 1H) ppm; C NMR (100.6 MHz, CDCl
C=O), 160.7 (Cq), 157.7 (Cq), 146.1 (CH), 134.4 (Cq), 131.4 (CH),
31.3 (CH), 129.1 (2CH), 129.0 (2CH), 128.4 (CH), 127.3 (Cq), 121.7
CH), 121.3 (CH), 116.0 (CH) ppm; HRMS m/z (ESI) positive ion,
3
): δ = 178.3
13
CH
186.8 (C=O), 166.4 (C=O), 159.3 (Cq), 157.6 (Cq), 133.1 (CH), 131.4
CH), 130.2 (Cq), 129.6 (2CH), 128.9 (CH), 128.4 (2CH), 121.4 (Cq),
21.1 (CH), 116.0 (CH), 59.2 (CH ), 39.2 (CH ) ppm; HRMS m/z (ESI)
positive ion, calculated for C17 13NNaO : [M+Na] 318.0742; Found:
2 2 3
), 3.67 (t, J= 6.2 Hz, 2H, CH ) ppm; C NMR (100.6 MHz, CDCl ): δ
=
(
1
+
2
2
calculated for C16
H
12NO
2
: [M+H] 250.0868; Found: 250.0872.
+
H
4
1
-(2,1-benzisoxazol-3-yl)octan-1-one (4cb): IR (KBr): 1683, 1292, 753
3
1
1
8
7
18.0743.
-(benzo[c]isoxazol-3-yl)-2-phenylethane-1,2-dione (4cj): IR (KBr):
-
1 1
cm ; H NMR (400 MHz, CDCl
3
): δ = 7.98 (dt, J= 8.8 Hz, J= 1.1 Hz, 1H),
7
6
3
6
.65 (ddd, J= 9.1 Hz, J= 1.2 Hz, J= 0.8 Hz, 1H), 7.32 (ddd, J= 9.1 Hz, J=
-1 1
3
737, 1674, 845 cm ; H NMR (400 MHz, CDCl ): δ = 8.09-8.06 (m, 2H),
.4 Hz, J= 1.1 Hz, 1H), 7.19 (ddd, J= 8.8 Hz, J= 6.5 Hz, J= 0.8 Hz, 1H),
.09 (t, J= 7.4 Hz, 2H), 1.80-1.70 (m, 2H), 1.38-1.18 (m, 8H), 0.82 (t, J=
.02 (dt, J= 8.8 Hz, J= 1.1 Hz, 1H), 7.82 (dt, J= 9.0 Hz, J= 1.0 Hz, 1H),
.72 (tt, J= 7.5 Hz, J= 1.3 Hz, 1H), 7.60-7.55 (m, 2H), 7.47 (ddd, J= 9.0
1
3
3
.9 Hz, 3H) ppm; C NMR (100.6 MHz, CDCl ): δ = 190.5 (C=O), 159.8
Hz, J= 6.5 Hz, J= 1.0 Hz, 1H), 7.38 (ddd, J= 8.8 Hz, J= 6.5 Hz, J= 0.8 Hz,
(
(
(
Cq), 157.6 (Cq), 131.2 (CH), 128.4 (CH), 121.3 (CH), 119.1 (Cq), 115.9
CH), 40.2 (CH ), 31.7 (CH ), 29.2 (CH ), 29.0 (CH ), 23.7 (CH ), 22.6
) ppm; HRMS m/z (ESI) positive ion, calculated for
13
1
1
1
3
H) ppm; C NMR (100.6 MHz, CDCl ): δ = 190.5 (C=O), 181.1 (C=O),
2
2
2
2
2
57.5 (Cq), 136.4 (Cq), 135.4 (CH), 134.5 (Cq), 131.5 (CH), 130.3 (2CH),
CH
2
), 14.1(CH
: [M+K] 284.1053; Found: 284.1050.
3
29.9 (CH), 129.2 (2CH), 125.2 (Cq), 120.5 (CH), 116.6 (CH) ppm;
+
C
15
H
19KNO
2
+
HRMS m/z (ESI) positive ion, calculated for
90.0220 Da; Found: 290.0218..
15 9 3
C H KNO : [M+K]
2
,1-benzisoxazol-3-yl(1-hydroxycyclohexyl)methanone (4cd): IR
2
-1 1
(
KBr): 3468, 1663, 1119, 870, 758 cm ; H NMR (400 MHz, CDCl
3
): δ =
.10 (dt, J= 8.8 Hz, J= 1.1 Hz, 1H), 7.76 (ddd, J= 9.1 Hz, J= 1.2 Hz, J=
.8 Hz, 1H), 7.43 (ddd, J= 9.1 Hz, J= 6.5 Hz, J= 1.0 Hz, 1H), 7.31 (ddd,
Silver-catalyzed oxidative cyclization of 2-(phenylethynyl)aniline 3a
with hydrogen peroxide. Synthesis of 3[hydroxy(phenyl)methylene]-
8
0
2
,1-benzisoxazol-1(3H)-ol (6): AgNO
(2.5 mL 50 wt. in O) were added to
phenyl)ethynyl)aniline 3a (0.113 g, 0.58 mmol) in CH
mixture was stirred at 60 °C and the reaction was monitored by TLC.
Then, the mixture after stirring for 0.5 h was cooled and 150 mL of H
and 150 mL of CH Cl were added. The organic layer was separated,
and the aqueous layer was extracted with CH Cl . The combined organic
3
(0.010 g, 0.058 mmol) and H
solution of 2-
OH (2.5 mL). The
2 2
O
J= 8.8 Hz, J= 6.5 Hz, J= 0.8 Hz, 1H), 3.63 (bs, 1H, OH), 2.36 (td, J= 12.8
1
3
%
H
2
a
Hz, J= 4.7 Hz, 2H), 1.91-1.70 (m, 8H) ppm; C NMR (100.6 MHz,
CDCl ): δ = 193.4 (C=O), 157.8 (C), 157.1 (C), 131.5 (CH), 129.1 (CH),
22.3 (C), 121.6 (CH), 116.0 (CH), 78.4 (COH), 33.8 (2CH ), 25.1 (CH ),
1.2 (2CH ppm; HRMS m/z (ESI) positive ion, calculated for
: [M+H] 246.1130; Found: 246.1130.
-(2,1-benzisoxazol-3-yl)-2-hydroxy-2-methylpropan-1-one (4ce): IR
(
3
3
1
2
2
2
2
O
2
)
+
2
2
14 3
C H16NO
2
2
1
layers were washed with water, dried over sodium sulfate, filtered and
concentrated. The filtrate was evaporated and subjected to column
chromatography on silica gel (eluent: hexane/EtOAc = 95:5) to givea
mixture of E- and Z-3-[hydroxy(phenyl)methylene]-2,1-benzisoxazol-
1(3H)-ol (6): (0.70 g, 50% yield). IR (KBr): 3414, 3125, 1612, 1216, 754,
-
1 1
(
KBr): 3478, 1663, 1287, 1170, 753 cm ; H NMR (400 MHz, CDCl
3
): δ =
.05 (dt, J= 8.8 Hz, J= 1.1 Hz, 1H), 7.71 (dt, J= 9.1 Hz, J= 1.0 Hz, 1H),
.38 (ddd, J= 9.0 Hz, J= 6.5 Hz, J= 1.1 Hz, 1H), 7.27 (ddd, J= 8.8 Hz, J=
8
7
6
1
3
.5 Hz, J= 0.8 Hz, 1H), 3.90 (bs, 1H, OH), 1.69 (s, 6H, CH
): δ = 193.2 (C=O), 157.3 (Cq), 157.1 (Cq),
31.5 (CH), 129.2 (CH), 122.2 (Cq), 121.4 (CH), 116.1 (CH), 76.3 (Cq),
6.7 (2CH ppm; HRMS m/z (ESI) positive ion, calculated for
: [M+K] 244.0376; Found: 244.0377.
-(2,1-benzisoxazol-3-yl)-2-hydroxy-2-methylbutan-1-one (4cf): IR
3
) ppm;
C
-
1 1
NMR (100.6 MHz, CDCl
1
2
3
701 cm ; H NMR (400 MHz, DMSO-d6): δ = 12.15 (s, 1 H, NOH), 8.71-
8.69 (m, 1 H), 8.06-8.04 (m, 1H), 7,96-7.93 (m, 2H), 7.67-7.55 (m, 4H),
1
3
7
.22-7.17 (m,1H), 3.87 (bs, 1H, OH) ppm; C NMR (100.6 MHz, DMSO-
d6): δ = 169.90 (C), 169.85 (C), 164.7 (C), 164.6 (C), 141.1 (C), 140.9
C), 134.50 (C), 134.45 (C), 134.3 (CH), 132.14 (CH), 132.13 (CH),
131.24 (CH), 131.23 (CH), 128.9 (CH), 127.0 (CH), 122.9 (CH), 119.9
CH), 119.8 (CH), 116.5 (C), 116.4 (C) ppm; HRMS m/z (ESI) positive ion,
3
)
+
11 3
C H12NO
(
1
1
1
(
(
1
KBr): 3524, 1668, 1190, 758 cm ; H NMR (400 MHz, CDCl
dt, J= 8.8 Hz, J= 1.1 Hz, 1H), 7.77 (ddd, J= 9.1 Hz, J= 1.2 Hz, J= 0.8 Hz,
H), 7.44 (ddd, J= 9.1 Hz, J= 6.5 Hz, J= 1.0 Hz, 1H), 7.33 (ddd, J= 8.8
Hz, J= 6.5 Hz, J= 0.8 Hz, 1H), 4.00 (bs, 1H, OH), 2.39-2.30 (m, 1H, CH ),
.10-2.01 (m, 1H, CH ), 1.73 (s, 3H, CH ), 0.85 (t, J= 7.5 Hz, 3H, CH
ppm; C NMR (100.6 MHz, CDCl ): δ = 193.7 (C=O), 157.4 (Cq), 157.2
Cq), 131.5 (CH), 129.3 (CH), 122.0 (Cq), 121.4 (CH), 116.1 (CH), 79.3
Cq), 32.5 (CH ), 25.4 (CH ), 7.8 (CH ) ppm; HRMS m/z (ESI) positive
: [M+H] 220.0974; Found: 220.0977.
-(6-chloro-2,1-benzisoxazol-3-yl)-2-hydroxy-2-methylbutan-1-one
3
): δ = 8.11
(
+
calculated for C14
Silver-catalyzed oxidative reaction of 4-(phenylethynyl)aniline (9)
with oxone: AgNO (0.014 g, 0.083 mmol) and oxone (1.020 g, 1.66
mmol) were added to a solution of 4-(phenylethynyl)aniline 9 (0.160 g,
0.83 mmol) in CH CN/H O (2.5 mL/2.5 mL). The mixture was stirred at
60 °C and the reaction was monitored by TLC. Then, the mixture after
stirring for 1.0 h was cooled and 150 mL of H O and 150 mL of CH Cl
were added. The organic layer was separated, and the aqueous layer
was extracted with CH Cl . The combined organic layers were washed
3
H11KNO : [M+K] 280.0376; Found: 280.0368.
2
3
2
2
3
3
)
1
3
3
3
2
(
(
2
2
2
2
3
3
+
ion, calculated for C12H14NO
3
1
2
2
-
1
1
with water, dried over sodium sulfate, filtered and concentrated. The
filtrate was evaporated and subjected to column chromatography on
silica gel (eluent: hexane/EtOAc = 90:10) to give:
(
4cg): IR (KBr): 3468, 1673, 1297, 1175, 809 cm ; H NMR (400 MHz,
CDCl ): δ = 8.07 (dd, J= 9.2 Hz, J= 0.9 Hz, 1H), 7.77 (dd, J= 1.6 Hz, J=
.9 Hz, 1H), 7.25 (dd, J= 9.2 Hz, J= 1.6 Hz, 1H), 3.90 (bs, 1H, OH), 2.31
td, J= 14.6 Hz, J= 7.4 Hz, 1H, CH ), 2.05 (td, J= 14.6 Hz, J= 7.6 Hz, 1H,
3
0
(
1
-nitroso-4-(phenylethynyl)benzene (10): (0.019 g, 19% yield); IR
1 1
2
(
3
KBr): 2207, 1114, 844, 758 cm ; H NMR (400 MHz, CDCl ): δ = 7.90-
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