(4-Dodecyl-2-thienyl)trimethylstannane → 4,7-Bis-(4-dodecyl-thiophen-2-yl)-5,6-dichloro-benzo[1,2,5]thiadiazole

HRID 335364Notes

Reaction equation

HRID 335364 reaction equation
[CH2:1]([C:13]1[CH:14]=[C:15]([C:18]2[C:23]3=[N:24][S:25][N:26]=[C:22]3[C:21](Br)=[C:20]([Cl:28])[C:19]=2[Cl:29])[S:16][CH:17]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].[CH2:30]([C:42]1[CH:43]=[C:44]([Sn](C)(C)C)[S:45][CH:46]=1)[CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH3:41]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.ClC1C=CC=CC=1>[CH2:1]([C:13]1[CH:14]=[C:15]([C:18]2[C:23]3=[N:24][S:25][N:26]=[C:22]3[C:21]([C:44]3[S:45][CH:46]=[C:42]([CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH3:41])[CH:43]=3)=[C:20]([Cl:28])[C:19]=2[Cl:29])[S:16][CH:17]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]

Participants

5

Reactant 2

HCID 53473953(4-Dodecyl-2-thienyl)trimethylstannaneHCID 675150854-(4-Dodecyl-thiophen-2-yl)-5,6-dichloro-7-bromo-benzo[1,2,5]thiadiazole

Product 1

HCID 675147024,7-Bis-(4-dodecyl-thiophen-2-yl)-5,6-dichloro-benzo[1,2,5]thiadiazoleYield 93%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 7964ChlorobenzeneSolvent

Conditions

Temperature
120 °C

Procedure

4-(4-Dodecyl-thiophen-2-yl)-5,6-dichloro-7-bromo-benzo[1,2,5]thiadiazole (0.530 g, 0.99 mmol), (4-dodecyl-thiophen-2-yl)-trimethyl-stannane (0.577 g, 1.39 mmol), and Pd(PPh3)2Cl2 (34.8 mg) were placed in a 100-mL Schlenk flask. The system was subjected to three quick vacuum-nitrogen cycles and 40 mL of anhydrous chlorobenzene was added. The mixture was heated at 120° C. for 17 hours. After the reaction was cooled down, the solvent was removed by rotary evaporation. The product was purified by silica gel column with chloroform/hexane (v/v, 1/1) as the eluent. The final product (650 mg, 92.8% yield) was obtained as an orange solid after being dried in vacuo. 1H NMR (CDCl3, 500 MHz): δ 7.49 (d, 2H, J=1.0 Hz), 7.22 (d, 2H, J=1.0 Hz), 2.72 (t, 4H, J=8.0 Hz), 1.71 (m, 4H), 1.27 (m, 36H), 0.89 (t, 6H, 7.0 Hz). 13C NMR (CDCl3, 500 MHz): δ 152.71, 143.12, 134.32, 134.23, 132.64, 126.42, 123.09, 31.97, 30.53, 30.46, 29.74, 29.72, 29.70, 29.67, 29.54, 29.42, 22.75, 14.19. Anal. calcd. for (C38H54Cl2N2S3): C, 64.65; H, 7.71; N, 3.97. Found: C, 64.72; H, 7.65; N, 3.98. m.p: 79-80° C.

Workup

  1. additionwas added
  2. temperatureAfter the reaction was cooled down
  3. customthe solvent was removed by rotary evaporation
  4. customThe product was purified by silica gel column with chloroform/hexane (v/v, 1/1) as the eluent

Sources & evidence

ORD record
ord-f649f8f016f1432abaa46bde02da5190
Source dataset
uspto-grants-2014_11
Patent number
US08883958B2

Reaction notes

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