Pyridine → 2-adamantyl Chloroformate

HRID 1457242Notes

Reaction equation

HRID 1457242 reaction equation
[CH:1]12[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH:2]1[OH:11])[CH2:8]2.[Cl:12][C:13]([O:16]C(=O)OC(Cl)(Cl)Cl)(Cl)Cl.N1C=CC=CC=1>ClCCl>[Cl:12][C:13]([O:11][CH:2]1[CH:3]2[CH2:9][CH:7]3[CH2:6][CH:5]([CH2:10][CH:1]1[CH2:8]3)[CH2:4]2)=[O:16]

Participants

5

Reactant 3

HCID 1049PyridineHCID 641492-AdamantanolHCID 94429Triphosgene

Product 1

HCID 108785372-adamantyl ChloroformateYield 251.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 2-adamantanol (10.1 g, 66.5 mmol) in dichloromethane (200 mL) was cooled in an ice bath. Bis(trichloromethyl)carbonate (triphosgene) (7.55 g, 25.4 mmol) was added followed by dropwise addition of pyridine (6.2 mL, 77 mmol) at such a rate that the temperature remained below 20° C. After a further 10 minutes the mixture was warmed to room temperature and stirred for a further 2.5 hours. The dichloromethane was removed in vacuo without heating and the residue slurried with ethyl acetate (50 mL). The pyridinium hydrochloride was filtered off and the filtrate evaporated to dryness without heating to yield 2-adamantylchloroformate (76) (13.7 g, 96%); δ H (300 M Hz, CDCl3, 1.48-2.32 (14H, m, adamantyl), 5.01 (1H, t, J 3 Hz, adamantyl 2-H); (lit.,2 δ H (CCl4) 1.3-2.4 (14H, m), 4.95 (lH, s).

Workup

  1. customremained below 20° C
  2. customThe dichloromethane was removed in vacuo
  3. temperaturewithout heating
  4. filtrationThe pyridinium hydrochloride was filtered off
  5. customthe filtrate evaporated to dryness
  6. temperaturewithout heating

Sources & evidence

ORD record
ord-36bdd4e25a18498ca3dc2096c1d28fde
Source dataset
uspto-grants-1998_12
Patent number
US05846942

Reaction notes

Loading…