Tetrahydrofuran → 5,10-Bis-dodecyloxy-2,7-bis-trimethylstannanyl-1,6-dithia-dicyclopenta[a,f]naphthalene

HRID 575499Notes

Reaction equation

HRID 575499 reaction equation
[CH2:1]([O:13][C:14]1[C:15]2[S:42][CH:41]=[CH:40][C:16]=2[C:17]2[CH:18]=[C:19]([O:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH3:39])[C:20]3[S:26][CH:25]=[CH:24][C:21]=3[C:22]=2[CH:23]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].C1COCC1.[Li+].CCC[CH2-].[CH3:53][Sn:54](Cl)([CH3:56])[CH3:55]>CCCCCC>[CH2:28]([O:27][C:19]1[C:20]2[S:26][C:25]([Sn:54]([CH3:56])([CH3:55])[CH3:53])=[CH:24][C:21]=2[C:22]2[CH:23]=[C:14]([O:13][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12])[C:15]3[S:42][C:41]([Sn:54]([CH3:56])([CH3:55])[CH3:53])=[CH:40][C:16]=3[C:17]=2[CH:18]=1)[CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH3:39]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 14016Trimethyltin chlorideHCID 61028n-Butyl lithiumHCID 712454095,10-Bis-dodecyloxy-1,6-dithia-dicyclopenta[a,f]naphthalene

Product 1

HCID 866765315,10-Bis-dodecyloxy-2,7-bis-trimethylstannanyl-1,6-dithia-dicyclopenta[a,f]naphthaleneYield 85.7%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

5,10-Bis-dodecyloxy-1,6-dithia-dicyclopenta[a,f]naphthalene (BB-3, 0.366 g, 0.6 mmol) was added into a 50 mL flask. The system was vacuumed and backfilled with argon 3 times before 17 mL of anhydrous THF was injected. N-Butyllithium (0.6 mL, 2.5 M in hexane, 1.5 mmol) was added after the mixture was cooled to −78° C. A white precipitate was observed after the mixture was stirred at −78° C. for 30 minutes. Stirring was continued at room temperature for one more hour before the mixture was cooled down to −78° C. again. Trimethyltin chloride (0.5 g, 2.5 mmol) was added in portions and stirring was continued overnight at room temperature. Hexane (100 mL) was added and the organic layer was washed with 150 mL of water. The aqueous layer was extracted with 50 mL of hexane twice. The combined organic layer was dried over anhydrous Na2SO4. Removal of the solvent under vacuum yielded a white solid. The colorless crystalline product (0.48 g, ˜85.7% yield) was obtained after recrystallization from a hexane/iso-propanol mixture. 1H NMR (CDCl3, 500 MHz): δ 7.80 (s, 2H), δ 7.51 (s, 2H), δ 4.37 (t, 4H, J=6.5 Hz), δ 2.00 (m, 4H), δ 1.63 (m, 4H), δ 1.46 (m, 4H), δ 1.30 (m, 28H), δ 0.90 (t, 6H, J=7.0 Hz), δ 0.51 (m, 18H).

Workup

  1. stirringStirring
  2. customwas continued at room temperature for one more hour before the mixture
  3. temperaturewas cooled down to −78° C. again
  4. stirringstirring
  5. waitwas continued overnight at room temperature
  6. washthe organic layer was washed with 150 mL of water
  7. extractionThe aqueous layer was extracted with 50 mL of hexane twice
  8. dry with materialThe combined organic layer was dried over anhydrous Na2SO4
  9. customRemoval of the solvent under vacuum
  10. customyielded a white solid

Sources & evidence

ORD record
ord-722635a5cb8d46fd8d501237a88997cd
Source dataset
uspto-grants-2015_05
Patent number
US09035004B2

Reaction notes

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