2,4,6-Trimethylpyridine → 3-(t-Butyldiphenylsiloxymethy)benzyl chloride

HRID 1648683Notes

Reaction equation

HRID 1648683 reaction equation
CS(Cl)(=O)=O.[O:6]([CH2:24][C:25]1[CH:26]=[C:27]([CH:30]=[CH:31][CH:32]=1)[CH2:28]O)[Si:7]([C:20]([CH3:23])([CH3:22])[CH3:21])([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.[Li+].[Cl-:34].CC1C=C(C)N=C(C)C=1>CN(C=O)C.O>[O:6]([CH2:24][C:25]1[CH:26]=[C:27]([CH:30]=[CH:31][CH:32]=1)[CH2:28][Cl:34])[Si:7]([C:20]([CH3:23])([CH3:22])[CH3:21])([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

7

Reactant 4

HCID 79532,4,6-TrimethylpyridineHCID 31297Methanesulfonyl chlorideHCID 433294Lithium ChlorideHCID 57049439(3-(((Tert-butyldiphenylsilyl)oxy)methyl)phenyl)methanol

Product 1

HCID 220737533-(t-Butyldiphenylsiloxymethy)benzyl chlorideYield 95.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Methanesulfonyl chloride (3.96 g, 34.6 mmol) was added dropwise to a stirred solution of 23 (11.8 g, 31.4 mmol), LiCl (1.33 g, 31.4 mmol), and s-collidine (4.19 g, 34.6 mmol) in anhydrous DMF (120 mL) at 0° C. under argon. The reaction mixture was allowed to warm to room temperature over 2 h, and was then poured into water and extracted twice with diethyl ether. The organic layers were combined and washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered, and concentrated to give 11.8 g (95%) of 24 as a clear, dark yellow liquid. The chloride was used without purification in the next reaction. 1H NMR (300 MHz, CDCl3) δ7.72-7.76 (m, 4H, ArH), 7.31-7.48 (m, 10H, ArH), 4.82 (s, 2H, CH2OSi), 4.62 (s, 2H, CH2C1), and 1.15 (s, 9H, SiC(CH3)3); 13C NMR (75 MHz, CDCl3) δ141.71, 137.35, 135.58, 135.51, 133.39, 129.74, 129.60, 128.64, 127.74, 127.08, 126.20, 126.06, 65.24 (CH2OSi), 46.34 (CH2C1), 26.84 (SiC(CH3)3), and 19.32 (SiC(CH3)3); MS (DCI) m/e 395 (MH+).

Workup

  1. extractionextracted twice with diethyl ether
  2. washwashed with saturated sodium chloride solution
  3. dry with materialdried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-d87aa8722a5c419ba5a66b12de5db13b
Source dataset
uspto-grants-1995_07
Patent number
US05436369

Reaction notes

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