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

HRID 1024824Notes

Reaction equation

HRID 1024824 reaction equation
Br[C:2]1[C:7]2=[N:8][S:9][N:10]=[C:6]2[C:5](Br)=[CH:4][C:3]=1[F:12].[CH2:13]([C:25]1[CH:26]=[C:27]([Sn](C)(C)C)[S:28][CH:29]=1)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[CH2:13]([C:25]1[CH:26]=[C:27]([C:2]2[C:7]3=[N:8][S:9][N:10]=[C:6]3[C:5]([C:27]3[S:28][CH:29]=[C:25]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH:26]=3)=[CH:4][C:3]=2[F:12])[S:28][CH:29]=1)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24]

Participants

5

Reactant 2

HCID 53473953(4-Dodecyl-2-thienyl)trimethylstannaneHCID 675153264,7-Dibromo-5-fluoro-2,1,3-benzothiadiazole

Product 1

HCID 675149464,7-Bis-(4-dodecyl-thiophen-2-yl)-5-fluoro-benzo[1,2,5]thiadiazoleYield 47%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
105 °C

Procedure

4,7-Dibromo-5-fluoro-benzo[1,2,5]thiadiazole (0.82 g, 2.63 mmol), (4-dodecyl-thiophen-2-yl)-trimethyl-stannane (2.72 g, 6.57 mmol), and Pd(PPh3)4 (50 mg) were combined into a 100-mL Schlenk flask. The system was vacuumed and backfilled with argon for three cycles before 50 mL of anhydrous toluene was added. The mixture was heated at 105° C. for 3 days. After the reaction was cooled down, the solvent was removed by rotary evaporation. The product was further purified by silica gel column with dichloromethane/hexane (v/v, 1/4) as the eluent. Removal of the solvent offered the final product (0.81 g, 47.0% yield) as a red powder after being dried in vacuo. 1H NMR (CDCl3, 500 MHz): δ 8.03 (d, 1H, J=1.0 Hz), δ 7.92 (d, 1H, J=1.0 Hz), δ 7.67 (d, 1H, J=15.0 Hz), δ 7.08 (d, 1H, J=1.0 Hz), δ 7.02 (d, 1H, J=1.0 Hz), δ 2.63 (m, 4H), δ 1.63 (m, 4H), δ 1.26 (m, 18H), δ 0.81 (t, 6H, 7.0 Hz).

Workup

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

Sources & evidence

ORD record
ord-04022b1b2dcb42a48681678eae68e17f
Source dataset
uspto-grants-2014_05
Patent number
US08723028B2

Reaction notes

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