Trifluoroacetic acid → HCID 21915695, compound

HRID 2427414Notes

Reaction equation

HRID 2427414 reaction equation
C(S[S:21][CH2:22][CH2:23][CH2:24][CH:25]([CH2:29][CH2:30][C:31]([OH:33])=[O:32])[C:26](O)=[O:27])(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.FC(F)(F)C(O)=O.C([SiH](CC)CC)C>ClCCl>[O:27]=[C:26]1[CH:25]([CH2:29][CH2:30][C:31]([OH:33])=[O:32])[CH2:24][CH2:23][CH2:22][S:21]1

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 86595783HCID 86595783, compound

Product 1

HCID 21915695HCID 21915695, compoundYield 37.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 2-[3-(tritylthio)mercaptopropyl]pentanedioic acid (150 g, 0.33 mol) in dichloromethane (500 mL) was added dropwise trifluoroacetic acid (110 mL) over 30 minutes. After being stirred for an additional 30 minutes, a solution of triethylsilane (45 mL, 0.33 mol) in dichloromethane (50 mL) was added and the mixture was stirred at 45° C. for 1 hour. The volatiles were removed in vacuo and the residue was triturated with hexanes (500 mL×2). The oily residue was dissolved in toluene (500 mL) containing 10-camphorsulfonic acid (14 g) and refluxed for 6 hours. The liberated water was removed using a Dean-Stork azeotropic adapter. Toluene was then distilled off and the residue was purified by silica gel chromatography (EtOAc/hexanes, 1/4). Subsequent recrystallization from EtOAc/hexanes afforded 23.3 g of 3-(2-oxotetrahydro-2H-thiopyran-3-yl)propanoic acid as a white solid (37% yield): 1H NMR (CD3OD) δ 1.65-1.78 (m, 2H), 2.05-2.18 (m, 4H), 2.35-2.48 (m, 2H), 2.65-2.74 (m, 1H), 3.13-3.29 (m, 2H); 13C NMR (CD3OD) δ 23.3, 27.4, 29.3, 31.2, 32.3, 50.0, 177.0, 206.4. Analysis calculated for C8H12O3S: C, 51.04; H, 6.43; S, 17.03. Found: C, 51.08; H, 6.38; S, 17.16.

Workup

  1. stirringthe mixture was stirred at 45° C. for 1 hour
  2. customThe volatiles were removed in vacuo
  3. customthe residue was triturated with hexanes (500 mL×2)
  4. dissolutionThe oily residue was dissolved in toluene (500 mL)
  5. additioncontaining 10-camphorsulfonic acid (14 g)
  6. temperaturerefluxed for 6 hours
  7. customThe liberated water was removed
  8. distillationToluene was then distilled off
  9. customthe residue was purified by silica gel chromatography (EtOAc/hexanes, 1/4)
  10. customSubsequent recrystallization from EtOAc/hexanes

Sources & evidence

ORD record
ord-db157e50f497446e9ac8ee5fbf007242
Source dataset
uspto-grants-2011_06
Patent number
US07968593B2

Reaction notes

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