Sodium hydride → HCID 86688389, compound

HRID 1621348Notes

Reaction equation

HRID 1621348 reaction equation
[H-].[Na+].[Br:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][O:12][CH2:13][C:14]1[S:15][C:16](=[C:19]2[S:23][CH:22]=[CH:21][S:20]2)[S:17][CH:18]=1.C(Br)C#C.C1CCN2C(=NCCC2)CC1>C1COCC1.C(Cl)(Cl)Cl>[Br:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][O:12][CH2:13][C:14]1[S:15][C:16](=[C:19]2[S:23][CH:22]=[CH:21][S:20]2)[S:17][CH:18]=1

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 86688390HCID 86688390, compound

Product 1

HCID 86688389HCID 86688389, compound

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Postfunctionalization of P1. To the solution of 37 mg (0.047 mmol) of P1 dissolved in 3 mL of anhydrous THF was added 0.9 mg (0.037 mmol) of NaH (60% in mineral oil) and stirred for half an hour under nitrogen atmosphere. Then to the mixture a solution of 20 mg (0.048 mmol) 4-(((8-bromooctyl)oxy)methyl)-2,2′-bi(1,3-dithiolylidene)/propargyl bromide in 0.2 mL of anhydrous THF was added followed by the addition of DBU (2 μL) in catalytic amount. The mixture was stirred for 48 h under nitrogen atmosphere. The reaction mixture was poured then into 100 mL water and extracted 3-4 times from 40 mL methylene chloride. The combined organic layer was dried over Na2SO4 and concentrated under reduced pressure to yield red solid. The solid was then dissolved in CHCl3, and reprecipitated in methanol 3-4 times. The polymer was then purified by washing it with hexane and methanol, followed by reprecipitating it again in methanol. The solid hence obtained was then dried under vacuum for 24 h. P2: Yield: 66%. Mn=11857, Mw/Mn=2.2. 1H NMR (400 MHz, CDCl3): δ 0.79 (b, 6H), 0.96-1.55 (b, 52H), 2.34 (b, 2H), 2.58 (b, 2H), 3.18 (b, 2H), 3.25 (b, 2H), 3.76 (b, 2H), 3.88 (b, 2H), 5.81 (b, 1H), 5.94 (b, 2H), 6.69-6.95 (b, 7H). P3: Yield: 80%. Mn=12228, Mw/Mn=2.41. 1H NMR (400 MHz, CDCl3): δ 0.87 (b, 6H), 1.26-1.69 (b, 40H), 2.51 (b, 1H), 2.77 (b, 4H), 4.28 (b, 2H), 4.70 (b, 2H), 7.07 (b, 4H), 7.14 (b, 3H).

Workup

  1. stirringThe mixture was stirred for 48 h under nitrogen atmosphere
  2. additionThe reaction mixture was poured
  3. extractioninto 100 mL water and extracted 3-4 times from 40 mL methylene chloride
  4. dry with materialThe combined organic layer was dried over Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customto yield red solid
  7. customreprecipitated in methanol 3-4 times
  8. customThe polymer was then purified
  9. washby washing it with hexane and methanol
  10. customby reprecipitating it again in methanol
  11. customThe solid hence obtained
  12. customwas then dried under vacuum for 24 h

Sources & evidence

ORD record
ord-cd306379fb3d48498a84ce422ab5017f
Source dataset
uspto-grants-2014_07
Patent number
US08772764B2

Reaction notes

Loading…