Diisopropylamine → Lithium diisopropylamide

HRID 931694

Reaction equation

HRID 931694 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]1[C:14]2[C:10](=[N:11][S:12][N:13]=2)[C:9]([C:15]2[S:16][CH:17]=[CH:18][CH:19]=2)=[CH:8][CH:7]=1.[CH:20]([NH:23][CH:24]([CH3:26])[CH3:25])([CH3:22])[CH3:21].[Li:27]CCCC.[CH3:32][Sn:33](Cl)([CH3:35])[CH3:34]>C1COCC1>[Li+:27].[CH3:21][CH:20]([N-:23][CH:24]([CH3:26])[CH3:25])[CH3:22].[CH3:32][Sn:33]([CH3:35])([CH3:34])[C:17]1[S:16][C:15]([C:9]2[C:10]3[C:14](=[N:13][S:12][N:11]=3)[C:6]([C:2]3[S:1][C:5]([Sn:33]([CH3:35])([CH3:34])[CH3:32])=[CH:4][CH:3]=3)=[CH:7][CH:8]=2)=[CH:19][CH:18]=1

Participants

7

Reactant 4

HCID 7912DiisopropylamineHCID 14016Trimethyltin chlorideHCID 3962944,7-Di(thiophen-2-yl)benzo(c)(1,2,5)thiadiazoleHCID 178418339Butyllithium

Product 2

HCID 2724682Lithium diisopropylamideHCID 581530092,1,3-Benzothiadiazole, 4,7-bis(5-(trimethylstannyl)-2-thienyl)-

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Compound (1) was dissolved in anhydrous THF (20 ml) in a nitrogen-filled flask. The solution was cooled down to −78° C. LDA was prepared from the reaction of diisopropylamine (0.5 g, 5.1 mmol, 3 eq.) and n-BuLi (3.12 ml, 5.1 mmol, 3 eq.) (1.6 M hexane solution) in anhydrous THF (2 ml), which was added to the above solution dropwise. After stirring for 1 h, trimethylstannyl chloride (3.8 ml, 3.8 mmol, 2.3 eq.) (1 M THF solution) was added and reacted for 1 h. The reaction was quenched by addition of water and the organic layer was extracted with ether, washed with water and dried over anhydrous magnesium sulfate. After the solvent was removed under reduced pressure, the residue was purified by recrystallization from ethanol, giving the title compound as a needle-shaped purple crystal.

Workup

  1. additionfilled flask
  2. additionwas added to the above solution dropwise
  3. customreacted for 1 h
  4. customThe reaction was quenched by addition of water
  5. extractionthe organic layer was extracted with ether
  6. washwashed with water
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customAfter the solvent was removed under reduced pressure
  9. customthe residue was purified by recrystallization from ethanol

Sources & evidence

ORD record
ord-4d36d403e34f4f5eb6ff3d944dfca4b1
Source dataset
uspto-grants-2016_03
Patent number
US09296864B2

Linked notes

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