Trimethyltin chloride → 4-Methyl-9-(trimethylstannyl)acridine

HRID 1365095Notes

Reaction equation

HRID 1365095 reaction equation
Br[C:2]1[C:3]2[C:8]([N:9]=[C:10]3[C:15]=1[CH:14]=[CH:13][CH:12]=[C:11]3[CH3:16])=[CH:7][CH:6]=[CH:5][CH:4]=2.[Li]CCCC.[Sn:22](Cl)([CH3:25])([CH3:24])[CH3:23]>C(OCC)C>[CH3:16][C:11]1[C:10]2[C:15](=[C:2]([Sn:22]([CH3:25])([CH3:24])[CH3:23])[C:3]3[C:8]([N:9]=2)=[CH:7][CH:6]=[CH:5][CH:4]=3)[CH:14]=[CH:13][CH:12]=1

Participants

5

Reactant 3

HCID 14016Trimethyltin chlorideHCID 85866300HCID 85866300, compoundHCID 178418339Butyllithium

Product 1

HCID 713742244-Methyl-9-(trimethylstannyl)acridineYield 84%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A solution of 9-bromo-4-methylacridine 9 (1 g, 3.7 mmol) in 50 ml anhydrous diethyl ether was cooled to −78° C. under nitrogen. To the solution was added 1.6 M n-BuLi in hexanes (0.74 mmol, 0.46 mL) dropwise over a period of 15 min and a 1.0 M solution of Me3SnCl in hexanes (0.81 mL, 0.81 mmol). The reaction solution mixture was allowed to warm to room temperature, stirred for 18 hours and concentrated in vacuo. Purification of the orange residue by flash chromatography (100:10:1 hexanes:ethyl acetate:triethyl amine) afforded 11 (1.1 g, 84%) as a yellow solid. GC-MS revealed contamination of the product with 5-10% 4-methylacridine that could not be separated by chromatography. The stannane was therefore employed in the Stille coupling with 1,8-dibromonaphthalene without further purification. 1H-NMR δ=0.67 (s, 9H), 2.95 (s, 3H), 7.41 (dd, J=6.9 Hz, J=8.8 Hz, 1H), 7.52 (ddd, J=1.4 Hz, J=6.5 Hz, J=6.5 Hz, 1H), 7.61 (d, J=6.9 Hz, 1H), 7.74 (ddd, J=1.4 Hz, J=7.4 Hz, J=7.4 Hz, 1H), 7.97 (d, J=7.9 Hz, 1H), 8.12 (d, J=9.3 Hz, 1H), 8.28 (d, J=7.9 Hz, 1H). 13C-NMR δ=−4.63, 19.51, 125.33, 125.56, 128.42, 128.94, 129.30, 129.93, 131.38, 133.49, 133.62, 138.58, 147.36, 147.53, 156.78.

Workup

  1. concentrationconcentrated in vacuo
  2. customPurification of the orange residue by flash chromatography (100:10:1 hexanes:ethyl acetate:triethyl amine)

Sources & evidence

ORD record
ord-e13693862ae94d01a96a2c3451d7c48b
Source dataset
uspto-grants-2011_02
Patent number
US07888509B2

Reaction notes

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