Hydrochloric Acid → HCID 12980033, compound

HRID 1796573Notes

Reaction equation

HRID 1796573 reaction equation
[CH:1]([C:4]1[CH:9]=[C:8]([CH:10]([CH3:12])[CH3:11])[CH:7]=[C:6]([CH:13]([CH3:15])[CH3:14])[C:5]=1[SH:16])([CH3:3])[CH3:2].[CH3:17][CH2:18][O-:19].[Na+].C(OC(OCC)CBr)C.Cl>CC(C)=O.O.C(O)C>[CH:13]([C:6]1[CH:7]=[C:8]([CH:10]([CH3:12])[CH3:11])[CH:9]=[C:4]([CH:1]([CH3:3])[CH3:2])[C:5]=1[S:16][CH2:17][CH:18]=[O:19])([CH3:15])[CH3:14]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 74852Ethane, 2-bromo-1,1-diethoxy-HCID 613579Benzenethiol, 2,4,6-tris(1-methylethyl)-HCID 2723922Sodium ethoxide

Product 1

HCID 12980033HCID 12980033, compound

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Na (0.35 g, 15 mmol) was added in small pieces under Ar to dry ethanol (7 mL). A solution of 2,4,6-triisopropylthiophenol (3.55 g, 15 mmol) was added to the solution of NaOEt and the resulting mixture stirred for 5 min at RT. Bromoacetaldehyde diethylacetal (2.5 mL, 16.5 mmol, Aldrich) was added dropwise to the solution of Na thiolate and the resulting mixture refluxed for 2 h. After that, it was poured into H2O (100 mL), extracted with CH2Cl2 (3×50 mL), the extracts dried (MgSO4), filtered and evaporated (aspirator). The NMR showed the presence of the product and ca. 15% of bromoacetaldehyde diethylacetal impurity. The crude reaction mixture was refluxed with 2% aq. HCl (20 mL) and acetone (30 mL) for 2 h 10 min. The reaction mixture was extracted with CH2Cl2 (3×50 mL), the extracts were dried (MgSO4), filtered and evaporated. Distillation of the product gave a clear liquid, bp 108–114C/0.5 mm, 3.58 g (85.6%). 1H NMR (CD2Cl2) 9.57 (t, 1H; J=3.4 Hz); 7.00 (s, 2H); 3.86 (septet, 2H; J=7.1 Hz); 3.33 (d, 2H; J=3.4 Hz); 2.87 (septet, 1H; J=7.0 Hz); 1.23 (d, 6H; J=7.0 Hz); 1.22 (d, 12H; J=7.1 Hz).

Workup

  1. temperaturethe resulting mixture refluxed for 2 h
  2. extractionextracted with CH2Cl2 (3×50 mL)
  3. dry with materialthe extracts dried (MgSO4)
  4. filtrationfiltered
  5. customevaporated (aspirator)
  6. customThe crude reaction mixture
  7. extractionThe reaction mixture was extracted with CH2Cl2 (3×50 mL)
  8. dry with materialthe extracts were dried (MgSO4)
  9. filtrationfiltered
  10. customevaporated
  11. distillationDistillation of the product
  12. customgave a clear liquid

Sources & evidence

ORD record
ord-e0a1a3fc7911440e960204cb0e4e7322
Source dataset
uspto-grants-2006_04
Patent number
US07030200B2

Reaction notes

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