The Journal of Organic Chemistry
Page 14 of 20
-
2
‐[(1Z)‐3‐imino‐2,3‐dihydro‐1H‐isoindol‐1‐ylidene]‐1‐(thio-
Compound [5a] . Isolated yield 772 mg (77 %); Mp: >300 ℃;
1
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
phen‐2‐yl)ethan‐1‐one (3c). Isolated yield 4.8 g (94 %); Mp:
169 – 171 ℃; H NMR (300 MHz, CDCl
3H), 7.66 – 7.62 (m, 2H), 7.17 (dd, JHH = 4.9 Hz, JHH = 3.8 Hz,
1H), 6.56 (s, 1H); C{ H} NMR (75 MHz, CDCl
1
9
H NMR (300 MHz, (CD ) CO-d ) 8.31 – 8.29 (m, 4H), 8.15
– 8.12 (m, 2H), 8.07 – 8.04 (m, 2H), 7.69 – 7.53 (m, 10H), 7.41
(s, 2H); C{ H} NMR (75 MHz, (CD ) CO-d ) 191.5, 165.3,
143.2, 141.8, 141.4, 133.2, 130.8, 130.4, 129.5, 129.1, 122.9,
3
2
6
1
3
) 7.87 -7.78 (m,
1
3
1
3
2
6
1
3
1
3
) 183.5,
-
51.4, 146.2, 136.3, 133.0, 131.7, 130.5, 128.3, 122.5, 121.4,
121.4, 102.7; HRMS (APCI-TOF) m/z: [M - H] Calcd for
1
1.5; H NMR (300 MHz, DMSO-d
6
) 10.92 (br.s., 1H), 9.10
C
32
H
20
N
3
O
2
478.1561; Found 478.1550.
(br.s., 1H), 8.21 – 8.19 (m, 2H), 7.98 – 7.93 (m, 2H), 7.74 –
-
7
1
1
9
2
.68 (m, 4H), 7.30 (dd, JHH = 4.9 Hz, JHH = 3.8 Hz, 1H), 6.99 (s,
Compound [5b] . Isolated yield 561 mg (50 %); Mp: >300
℃; H NMR (300 MHz, (CD ) CO-d ) 8.33 (d, JHH = 8.9 Hz,
3 2 6
4H), 8.11 – 8.10 (m, 2H), 8.04 – 8.03 (m, 2H), 7.59 – 7.50 (m,
4H), 7.39 (s, 2H), 7.13 (d, JHH = 8.9 Hz, 4H), 3.94 (s, 6H);
C{ H} NMR (75 MHz, (CD ) CO-d ) 190.0, 164.6, 164.3,
43.4, 141.9, 134.2, 131.4, 130.5, 130.2, 122.8, 121.3, 114.6,
102.7, 55.9; HRMS (APCI-TOF) m/z: [M - H] Calcd for
1
3
1
1
H); C{ H} NMR (75 MHz, CDCl
3
) 182.5, 160.0, 150.6,
46.6, 136.6, 134.0, 131.6, 131.5, 131.4, 128.7, 122.4, 122.2,
0.8; HRMS (APCI-TOF) m/z: [M - H] Calcd for C14
53.0441; Found 253.0414.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
-
10 2
H N OS
13
1
3
2
6
1
-
General procedure for the synthesis of compounds 4a-c
To the solution of isoindol-1-imines 3a-c (4 mmol) in ethanol
(40 mL), concentrated hydrochloric acid (2 mL) was added. The
resulting mixture was refluxed for 8 hours. After cooling to
room temperature, the solution was diluted with water (40 mL)
and stirred for another 30 min. Then, the resulting precipitate
was collected by filtration and air dried to give pure isoindolin-
C
34
H
24
N
3
O
4
538.1772; Found 538.1761.
-
Compound [5c] . Isolated yield 822 mg (81 %); Mp: >300
℃; H NMR (300 MHz, (CD
1
3
)
2
CO-d
6
) 8.27 (dd, JHH = 3.8 Hz,
J
7
7
HH = 1.1 Hz, 2H), 8.11 – 8.09 (m, 2H), 8.06 – 8.03 (m, 2H),
.93 (dd, JHH = 5.0 Hz, JHH = 1.1 Hz, 2H), 7.60 – 7.51 (m, 4H),
.32 – 7.29 (m, 4H); C{ H} NMR (75 MHz, (CD ) CO-d )
3 2 6
184.0, 176.6, 165.0, 149.5, 143.06, 141.9, 134.8, 132.4,
130.8, 130.4, 129.4, 129.2, 123.0, 121.4, 102.7; HRMS (APCI-
1
3
1
1
-ones 4a-c.
(3Z)‐3‐(2‐oxo‐2‐phenylethylidene)‐2,3‐dihydro‐1H‐isoin-
-
dol‐1‐one(4a). Isolated yield 747 mg (75 %); Mp: 164 – 166
TOF) m/z: [M - H] Calcd for C H N O S 490.0689; Found
490.0676.
2
8
16
3
2 2
1
℃
(
(
1
1
; H NMR (300 MHz, CDCl
3
) 10.61 (s, 1H), 8.06 – 8.03
m, 2H), 7.93 – 7.90 (m, 1H), 7.85 – 7.83 (m, 1H), 7.72 – 7.50
m, 5H), 6.89 (s, 1H); 13C{ H} NMR (75 MHz, CDCl
1
3
) 191.2,
General procedure for the synthesis of compounds 5a-c
The suspension of anionic dye [5a-c] (0.5 mmol) in dry ethanol
(8 mL) was treated with glacial acetic acid (1 mmol, 60 mg, 2
eq.) and stirred for 1 hour at room temperature. The resulting
brown precipitate was collected by filtration and vacuum dried.
-
69.2, 148.6, 138.6, 137.3, 133.1, 133.0, 132.1, 129.5, 128.9,
28.1, 124.4, 121.3, 94.9HRMS (APCI-TOF) m/z: [M - H]
2
Calcd for C16H11NO 248.0717; Found 248.0688.
-
(3Z)‐3‐[2‐(4‐methoxyphenyl)‐2‐oxoethylidene]‐2,3‐dihydro‐
1H‐isoindol‐1‐one (4b). Isolated yield 860 mg (77 %); Mp: 182
Compound 5a. Isolated yield 139 mg (58 %); Mp: 200 – 202
℃; H NMR (300 MHz, (CDCl
(m, 4H), 8.09 – 8.06 (m, 2H), 7.88 – 7.85 (m, 2H), 7.61 – 7.58
(m, 4H), 7.52 – 7.43 (m, 6H), 7.07 (s, 2H); C{ H} NMR (75
1
1
–
8
7
184 ℃; H NMR (300 MHz, CDCl
3
) 10.64 (s, 1H), 8.07 –
3
) 13.38 (s, 1H), 8.15 – 8.12
.02 (m, 2H), 7.92 – 7.89 (m, 1H), 7.85 – 7.82 (m, 1H), 7.71 –
.61 (m, 2H), 7.02 – 6.98 (m, 2H), 6.86 (s, 1H), 3.90 (s, 3H);
C{ H} NMR (75 MHz, CDCl
37.4, 132.9, 131.9, 131.5, 130.5, 129.5, 124.4, 121.1, 114.1,
1
3
1
1
3
1
3
) 189.7, 169.2, 163.7, 147.9,
MHz, (CDCl
3
) 190.8, 167.6, 151.9, 138.7, 136.3, 133.1,
1
9
132.9, 132.7, 132.3, 130.9, 130.6, 129.2, 128.9, 128.9, 128.8,
128.4, 128.2, 123.0, 121.5, 121.5, 120.9, 106.8, 97.0; HRMS
(APCI positive) Calcd for C32
Found 480.1702.
-
4.9, 55.7; HRMS (APCI-TOF) m/z: [M - H] Calcd for
+
C
17
H13NO
3
278.0823; Found 278.0847.
H
21
N
3
O
2
[M + H] : 480.1707,
(3Z)‐3‐[2‐oxo‐2‐(thiophen‐2‐yl)ethylidene]‐2,3‐dihydro‐1H‐
isoindol‐1‐one (4c). Isolated yield 867 mg (85 %); Mp: 220 –
Compound 5b. Isolated yield 172 mg (64 %); Mp: 164 – 166
℃
1
222 ℃; H NMR (300 MHz, CDCl
3
) 10.47 (s, 1H), 7.92 –
1
; H NMR (300 MHz, CDCl
3
) 13.34 (s, 1H), 8.13 – 8.10
7.89 (m, 1H), 7.86 -7.82 (m, 2H), 7.72 – 7.62 (m, 3H) 7.21 (dd,
(m, 4H), 8.08 – 8.05 (m, 2H), 7.84 -7.84 (m, 2H), 7.59 – 7.57
1
3
1
J
1
= 4.9 Hz, J
MHz, CDCl ) 183.4, 168.9, 148.2, 145.8, 137.0, 134.1, 133.0,
32.1, 131.4, 129.5, 128.5, 124.4, 121.3, 95.3; HRMS (APCI-
TOF) m/z: [M - H] Calcd for C14
54.0257.
2
= 3.8 Hz, 1H), 6.70 (s, 1H); C{ H} NMR (75
13
1
(m, 4H), 7.01 (s, 2H), 6.94 – 6.91 (m, 4H), 3.82 (s, 6H); C{ H}
NMR (75 MHz, CDCl ) 189.5, 167.3, 163.4, 151.2, 138.8,
136.3, 131.9, 131.6, 130.8, 130.4, 122.9, 120.8, 113.6, 107.1,
3
3
1
-
H
9
NO
2
S 254.0281; Found
+
5
5
5.6; HRMS (APCI positive) Calcd for C34
40.1918, Found 540.1916.
25 3 4
H N O [M + H] :
2
General procedure for the synthesis of dyes [5a-c]-:
To the solution of isoindol-1-imines 3a-c (4 mmol) in dry 1,4-
dioxane (100 mL), sodium hydride dust (2.4 mmol, 58 mg, 0.6
eq.) was added under argon atmosphere. The solution was
stirred for 5 min at room temperature, then under reflux condi-
tions for 2h. After cooling to room temperature the resulting in-
tense purple solution was diluted with dry hexane (100 mL) and
left for 3 hours for the crystallization. After 3 h, the resulting
black product was filtered off, washed with dry hexane, and
dried under high vacuum.
Compound 5c. Isolated yield 135 mg (55 %); Mp: 174 – 176
℃
1
3
; H NMR (300 MHz, CDCl ) 13.25 (s, 1H), 8.08 – 8.06
(
(
(
m, 2H), 7.90 (dd, JHH = 3.8 Hz, JHH = 1.0 Hz, 2H), 7.86 – 7.82
m, 2H), 7.65 (dd, JHH = 4.9 Hz, JHH = 1.0 Hz, 2H), 7.60 – 7.56
m, 4H), 7.13 (dd, JHH = 4.9 Hz, JHH = 3.8 Hz, 2H), 6.93 (s, 2H);
C{ H} NMR (75 MHz, CDCl
38.7, 1363, 133.8, 132.6, 131.0, 130.6, 128.0, 123.0, 120.9,
06.7; HRMS (APCI positive) Calcd for C28 [M +
13
1
3
) 182.8, 167.6, 151.7, 146.3,
1
1
17 3 2 2
H N O S
+
H] :492.0835, Found 492.0838.
ACS Paragon Plus Environment