2,2,6,6-Tetramethylpiperidine → 2,1,3-Benzothiadiazole, 4,7-bis(5-(trimethylstannyl)-2-thienyl)-

HRID 1618065

Reaction equation

HRID 1618065 reaction equation
CC1(C)CCCC(C)(C)N1.C([Li])CCC.[S:16]1[CH:20]=[CH:19][CH:18]=[C:17]1[C:21]1[C:29]2[C:25](=[N:26][S:27][N:28]=2)[C:24]([C:30]2[S:31][CH:32]=[CH:33][CH:34]=2)=[CH:23][CH:22]=1.[CH3:35][Sn:36](Cl)([CH3:38])[CH3:37]>C1COCC1.C(OCC)C.O>[CH3:35][Sn:36]([CH3:38])([CH3:37])[C:32]1[S:31][C:30]([C:24]2[C:25]3[C:29](=[N:28][S:27][N:26]=3)[C:21]([C:17]3[S:16][C:20]([Sn:36]([CH3:38])([CH3:37])[CH3:35])=[CH:19][CH:18]=3)=[CH:22][CH:23]=2)=[CH:34][CH:33]=1

Participants

8

Reactant 4

HCID 130352,2,6,6-TetramethylpiperidineHCID 14016Trimethyltin chlorideHCID 3962944,7-Di(thiophen-2-yl)benzo(c)(1,2,5)thiadiazoleHCID 178418339Butyllithium

Product 1

HCID 581530092,1,3-Benzothiadiazole, 4,7-bis(5-(trimethylstannyl)-2-thienyl)-

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A mechanically stirred solution of 2,2,6,6-tetramethylpiperidine (TMP) (0.55 g, 4 mmol) in dry THF (25 mL) under argon was cooled to −78° C. Next, n-butyllithium (3.9 mmol) was rapidly added to the solution. The resulting solution was allowed to warm to room temperature. It was kept at room temperature for 10 min and subsequently cooled to −78° C. again. A solution of 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole in 5 mL of dry THF was then added drop-wise to the cooled solution. The resulting solution has a deep purple color and was stirred at −78° C. for 30 min. A 1M solution of trimethyltin chloride in hexanes (3.9 mL) was then added. The reaction mixture was allowed to warm to room temperature and stirred overnight. Water was added to quench the reaction. Diethyl ether was added, and the mixture was washed 3 times with 0.1M HCl to remove the TMP. The solution was then dried with MgSO4. The solvent was removed, and the final product (0.42 g, 45%) was re-crystallized in ethanol to yield orange needles. 1H NMR (CDCl3): 8.19 (d, 2H), 7.88 (s, 2H), 7.30 (d, 2H), 0.44 (s, 18H). 13C NMR (CDCl3): 152.7, 145.1, 140.2, 136.1, 128.4, 125.9, 125.8, −8.2.

Workup

  1. temperaturesubsequently cooled to −78° C. again
  2. temperatureto warm to room temperature
  3. stirringstirred overnight
  4. customto quench
  5. customthe reaction
  6. washthe mixture was washed 3 times with 0.1M HCl
  7. customto remove the TMP
  8. dry with materialThe solution was then dried with MgSO4
  9. customThe solvent was removed
  10. customthe final product (0.42 g, 45%) was re-crystallized in ethanol
  11. customto yield orange needles

Sources & evidence

ORD record
ord-06a7dc626ae04ef7b4828cb706317178
Source dataset
uspto-grants-2014_07
Patent number
US08765968B2

Linked notes

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