Triethylamine → Silanol, (1,1-dimethylethyl)diphenyl-

HRID 1582213Notes

Reaction equation

HRID 1582213 reaction equation
BrCCCCC[OH:7].CCN(CC)CC.[CH3:15][C:16]([Si:19](Cl)([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)([CH3:18])[CH3:17].[NH4+].[Cl-]>C(Cl)Cl.CN(C1C=CN=CC=1)C>[Si:19]([OH:7])([C:16]([CH3:18])([CH3:17])[CH3:15])([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 25517Ammonium ChlorideHCID 94078tert-ButyldiphenylchlorosilaneHCID 1187091-Pentanol, 5-bromo-

Product 1

HCID 608071Silanol, (1,1-dimethylethyl)diphenyl-Yield 155.3%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of 5-bromo-pentanol (0.9889 g, 5.9 mmol, 1 eq) in anhydrous CH2Cl2 (20 mL) under N2 at 25° C. was treated with anhydrous Et3N (1.0 mL, 7.2 mmol, 1.2 eq), TBDPSCl (1.7 mL, 6.5 mmol, 1.1 eq) and DMAP (0.23 g, 1.9 mmol, 0.3 eq). The reaction mixture was stirred for 2 h before an aqueous solution of saturated NH4Cl (100 mL) was added. The aqueous layer was extracted with EtOAc (3×100 mL) and the organic layers were dried (Na2SO4), filtered, and concentrated in vacuo. The crude product was chromatographed (SiO2, 5×20 cm, 0-20% EtOAc/hexanes, gradient elution) to afford TBDPSOH (2.35 g, 98%) as a clear oil; 1H NMR (CDCl3, 400 MHz) δ 7.66-7.60 (m, 4H), 7.44-7.33 (m, 6H), 3.64 (t, 2H, J=6.1 Hz), 3.37 (t, 2H, J=6.9 Hz), 1.82 (p, 2H, J=7.3 Hz), 1.59-1.45 (m, 4H), 1.03 (s, 9H); 13C NMR (CDCl3, 100 MHz) δ 135.6, 129.6, 127.6, 127.5, 63.5, 33.9, 32.5, 31.6, 26.8, 24.5, 19.2; IR (film) υmax 3069, 2930, 2856, 2359, 1470, 1427, 1389, 1106, 822, 738, 700 cm−1; FABHRMS (NBA-CsI) m/z 537.0235 (C21)H29OSiBr+Cs+ requires 537.0225).

Workup

  1. additionwas added
  2. extractionThe aqueous layer was extracted with EtOAc (3×100 mL)
  3. dry with materialthe organic layers were dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude product was chromatographed
  7. wash(SiO2, 5×20 cm, 0-20% EtOAc/hexanes, gradient elution)

Sources & evidence

ORD record
ord-9df490d0d1ff4e3e9b1bb22c5eb7fd13
Source dataset
uspto-grants-2004_05
Patent number
US06734204B1

Reaction notes

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