p-Toluidine → N-(4-Methylphenyl)-1,1-dimethyl-1-(2-methyl-1H-inden-7-yl)silanamine

HRID 557498Notes

Reaction equation

HRID 557498 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.[Li]CCCC.Cl[Si:15]([CH3:27])([CH3:26])[C:16]1[CH:17]=[CH:18][CH:19]=[C:20]2[C:24]=1[CH2:23][C:22]([CH3:25])=[CH:21]2>C1COCC1>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([NH:1][Si:15]([CH3:26])([CH3:27])[C:16]2[CH:17]=[CH:18][CH:19]=[C:20]3[C:24]=2[CH2:23][C:22]([CH3:25])=[CH:21]3)=[CH:3][CH:4]=1

Participants

5

Reactant 3

HCID 7813p-ToluidineHCID 58418828chloro(dimethyl)(2-methyl-1H-inden-7-yl)silaneHCID 178418339Butyllithium

Product 1

HCID 58418709N-(4-Methylphenyl)-1,1-dimethyl-1-(2-methyl-1H-inden-7-yl)silanamine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 6.44 g (60.0 mmol) of p-toluidine in 180 mL of THF 24.0 mL (60.0 mmol) of 2.5 M nBuLi in hexanes was added at 0° C. This mixture was additionally stirred for 4 hours at room temperature, then cooled to −40° C., and a solution of 13.4 g (60.0 mmol) of chloro(dimethyl)(2-methyl-1H-inden-7-yl)silane in 50 mL of THF was added in one portion. The resulting mixture was stirred for 12 hours at room temperature and then evaporated to dryness. To the residue 100 mL of ether was added, and the obtained suspension was stirred for 20 minutes, and then filtered through glass frit (G3). The precipitate was additionally washed with 2×100 mL of ether. The combined filtrate was evaporated to dryness, and the residue was washed with 2×15 mL of cold hexanes and then dried in vacuum. Yield 11.3 g (64%) of white solid. 1H NMR (CD2Cl2): δ 7.40 (dd, J=7.3 Hz, J=1.3 Hz, 1H, 6-H in indenyl), 7.32 (dd, J=7.3 Hz, J=1.3 Hz, 1H, 4-H in indenyl), 7.26 (t, J=7.3 Hz, 1H, 5-H in indenyl), 6.88-6.91 (m, 2H, 2,6-H in p-tolyl), 6.53-6.57 (m, 2H, 3,5-H in p-tolyl), 6.52 (m, 1H, 3-H in indenyl), 3.68 (br.s, 1H, NH), 3.40 (s, 2H, 1,1′-H in indenyl), 2.20 (s, 3H, 4-Me in p-tolyl), 2.16 (m, 3H, 2-Me in indenyl), 0.57 (s, 6H, SiMe2). Anal. Calc. for C19H23NSi: C, 77.76; H, 7.90; N, 4.77%. Found: C, 77.94; H, 8.05; N, 4.94%.

Workup

  1. temperaturecooled to −40° C.
  2. stirringThe resulting mixture was stirred for 12 hours at room temperature
  3. customevaporated to dryness
  4. additionTo the residue 100 mL of ether was added
  5. stirringthe obtained suspension was stirred for 20 minutes
  6. filtrationfiltered through glass frit (G3)
  7. washThe precipitate was additionally washed with 2×100 mL of ether
  8. customThe combined filtrate was evaporated to dryness
  9. washthe residue was washed with 2×15 mL of cold hexanes
  10. customdried in vacuum

Sources & evidence

ORD record
ord-4f884e62b56e479e9486c2a5c7e3a30d
Source dataset
uspto-grants-2011_11
Patent number
US08058461B2

Reaction notes

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