Hydrochloric Acid → HCID 70191672, compound

HRID 1740222Notes

Reaction equation

HRID 1740222 reaction equation
[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6]O)=[CH:4][CH:3]=1.C(N([CH2:15][CH3:16])CC)C.[C:17]([Si:21](Cl)([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)([CH3:20])([CH3:19])[CH3:18].Cl.[OH2:36]>CN(C)C=O.C(OCC)C>[Br:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][C:16]2[CH:15]=[CH:31][CH:30]=[CH:29][C:28]=2[Si:21]([O:36][Si:21]([C:17]([CH3:20])([CH3:19])[CH3:18])([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[CH2:6][C:5]2[CH:8]=[CH:9][C:2]([Br:1])=[CH:3][CH:4]=2)([C:17]([CH3:18])([CH3:19])[CH3:20])[C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)=[CH:4][CH:3]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 962WaterHCID 8471TriethylamineHCID 701194-Bromobenzyl alcoholHCID 94078tert-Butyldiphenylchlorosilane

Product 1

HCID 70191672HCID 70191672, compoundYield 93%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 28.2 g (0.150 mol) of 4-bromobenzylalcohol in 470 mL of dry dimethylformamide under nitrogen atmosphere was added 31.4 mL (0.225 mol) of triethylamine. The reaction mixture was cooled to 0° C. and 43 mL (0.17 mol) of t-butyl-chlorodiphenylsilane was added dropwise by addition funnel. The reaction mixture was stirred at ambient temperature overnight then poured into a separatory funnel containing 1 L of diethyl ether and 500 mL of water. To this mixture was added 125 mL of 2N aqueous hydrochloric acid. The layers were separated and the aqueous layer was extracted with diethyl ether (2×350 mL). The organic extracts were combined, washed with water (2×250 mL) and dried over magnesium sulfate. The solids were removed by filtration and the solvent removed under vacuum to give an oil which crystallized on standing. The flask containing the crude product was placed in the freezer overnight then triturated with a minimal amount of methanol and filtered. The solid was air dried for several hours then dried under vaccuum overnight to afford 59.5 g (93%) of product as an off-white solid (mp 44-47° C.). 1H NMR (200 MHz, CDCl3): δ 1.15 (s, 9H), 4.76 (s, 2H), 7.25 (d, 8 Hz, 2H), 7.45 (m, 8H), 7.75 (m, 4H). FAB-MS: calculated for C23H25BrOSi 424; found 425 (M+H, 7%).

Workup

  1. additionthen poured into a separatory funnel
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with diethyl ether (2×350 mL)
  4. washwashed with water (2×250 mL)
  5. dry with materialdried over magnesium sulfate
  6. customThe solids were removed by filtration
  7. customthe solvent removed under vacuum
  8. customto give an oil which
  9. customcrystallized
  10. additionThe flask containing the crude product
  11. customwas placed in the freezer overnight
  12. customthen triturated with a minimal amount of methanol
  13. filtrationfiltered
  14. customdried for several hours
  15. customthen dried under vaccuum overnight

Sources & evidence

ORD record
ord-f48b83dc5e4e4fb4b30869831ed4ebde
Source dataset
uspto-grants-1999_10
Patent number
US05968924

Reaction notes

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