Tributyltin Chloride → N,N-Dimethyl-6-(tributylstannyl)pyridin-2-amine

HRID 2079756Notes

Reaction equation

HRID 2079756 reaction equation
Br[C:2]1[N:7]=[C:6]([N:8]([CH3:10])[CH3:9])[CH:5]=[CH:4][CH:3]=1.C([Li])CCC.[CH2:16]([Sn:20](Cl)([CH2:25][CH2:26][CH2:27][CH3:28])[CH2:21][CH2:22][CH2:23][CH3:24])[CH2:17][CH2:18][CH3:19]>BrC1C=C2C(=CC=1)NN=C2.O1CCCC1.C(=O)(O)[O-].[Na+].C(OCC)(=O)C>[CH3:9][N:8]([CH3:10])[C:6]1[CH:5]=[CH:4][CH:3]=[C:2]([Sn:20]([CH2:21][CH2:22][CH2:23][CH3:24])([CH2:25][CH2:26][CH2:27][CH3:28])[CH2:16][CH2:17][CH2:18][CH3:19])[N:7]=1

Participants

8

Reactant 3

HCID 15096Tributyltin ChlorideHCID 140060626-bromo-N,N-dimethylpyridin-2-amineHCID 178418339Butyllithium

Product 1

HCID 57813708N,N-Dimethyl-6-(tributylstannyl)pyridin-2-amineYield 50%

Reagents, catalysts & solvents 4

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×HCID 516892Sodium BicarbonateSolventHCID 7619295-bromo-1H-indazoleSolvent

Conditions

Temperature
0 °C

Procedure

Add dropwise a solution of (6-bromo-pyridin-2-yl)-dimethyl-amine (8; g, 39.8 mmol) in anhydrous tetrahydrofuran (10; mL) to a stirring cooled solution of n-butyl-lithium in hexanes (2.5; M, 19.1; mL, 47.7; mmol) in anhydrous tetrahydrofuran (160; mL) under nitrogen at −75° C. at a rate so that the internal reaction temperature does not exceed −70° C. After 1; h at −75° C., add dropwise tri-n-butyltin chloride (13; g, 39.8; mmol), stir for 30; min and warm to 0° C. Add water (200; mL) and then dilute with a saturated aqueous solution of sodium bicarbonate (50; mL) and diethyl ether (200; mL) and separate the layers. Extract the organic phase once with brine (200; mL), dry over sodium sulfate, filter and concentrate to give a liquid (25.4; g). Purify by silica gel chromatography eluting with iso-hexane:ethyl acetate:triethylamine 90:9:1, to give the title product as a colorless liquid (8.16; g, 50%). MS (m/z): 409-414; cluster (M+1).

Workup

  1. customdoes not exceed −70° C
  2. customseparate the layers
  3. extractionExtract the organic phase once with brine (200; mL)
  4. dry with materialdry over sodium sulfate
  5. filtrationfilter
  6. concentrationconcentrate
  7. customto give a liquid (25.4; g)
  8. customPurify by silica gel chromatography
  9. washeluting with iso-hexane:ethyl acetate:triethylamine 90:9:1

Sources & evidence

ORD record
ord-d1515cf47eb64258b5eead162463d42d
Source dataset
uspto-grants-2011_04
Patent number
US07932274B2

Reaction notes

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