Ethyl Thioglycolate → HCID 68454232, compound

HRID 2353592Notes

Reaction equation

HRID 2353592 reaction equation
Cl[C:2](=[C:5]1[C:10](=O)[CH2:9][C@H:8]2[C@@H:6]1[C:7]2([CH3:13])[CH3:12])[CH2:3][CH3:4].C([O:16][C:17](=[O:20])[CH2:18][SH:19])C>C1COCC1.C(O)C.CC(=O)OCC>[CH2:3]([C:2]1[S:19][C:18]([C:17]([OH:20])=[O:16])=[C:10]2[C:5]=1[CH:6]1[C:7]([CH3:13])([CH3:12])[CH:8]1[CH2:9]2)[CH3:4]

Participants

6

Reactant 2

HCID 12185Ethyl ThioglycolateHCID 68451881HCID 68451881, compound

Product 1

HCID 68454232HCID 68454232, compoundYield 27.5%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
30 °C

Procedure

To a solution of (1R,5S)-2-[1-chloro-propylidene]-6,6-dimethyl-bicyclo[3.1.0]hexan-3-one (11.0 g, 55.4 mmol) in THF (40 mL) a solution of ethyl-2-mercaptoacetate (9.6 mL, 87.2 mmol) in a freshly prepared solution of Na (3.9 g, 170 mmol) in ethanol (95 mL) is added at 30° C. The reaction mixture is stirred at 30° C. for 2 h before it is diluted with EA and washed with 1 N aq. NaOH and brine. The organic extracts are dried over Na2SO4 and the solvent is removed in vacuo. The resulting brown oil (9.66 g) is dissolved in ethanol (365 mL) and diluted with 1 N aq. LiOH (365 mL). The mixture is refluxed for 1 h before the organic solvent is removed in vacuo. Solid material is filtered off and the filtrate is extracted twice with diethyl ether. The organic layer is extracted back with 1 N aq. LiOH and brine. The aq. extracts are acidified with aq. HCl (37%). The precipitate that formes is collected, washed with water followed by hexane, and dried under high vacuum to give rac-(1aS,5aR)-2-ethyl-1,1-dimethyl-1,1a,5,5a-tetrahydro-3-thia-cyclopropa[a]pentalene-4-carboxylic acid (3.6 g) as beige crystals. From the hexane washings a second crop (2.37 g) is obtained after evaporation of the solvent; LC-MS: tR=0.99 min, [M+1]+=237.24, 1H NMR (CDCl3): δ 3.00 (dd, J=5.9, 19.3 Hz, 1H), 2.84-2.70 (m, 3H), 1.92-1.86 (m, 2H), 1.28 (t, J=7.0 Hz, 3H), 1.12 (s, 3H), 0.70 (s, 3H).

Workup

  1. washwashed with 1 N aq. NaOH and brine
  2. dry with materialThe organic extracts are dried over Na2SO4
  3. customthe solvent is removed in vacuo
  4. dissolutionThe resulting brown oil (9.66 g) is dissolved in ethanol (365 mL)
  5. additiondiluted with 1 N aq. LiOH (365 mL)
  6. temperatureThe mixture is refluxed for 1 h before the organic solvent
  7. customis removed in vacuo
  8. filtrationSolid material is filtered off
  9. extractionthe filtrate is extracted twice with diethyl ether
  10. extractionThe organic layer is extracted back with 1 N aq. LiOH and brine
  11. customThe precipitate that formes is collected
  12. washwashed with water
  13. customdried under high vacuum

Sources & evidence

ORD record
ord-be6a9c06980c44c6ad01f3a29a1aa8e9
Source dataset
uspto-grants-2010_07
Patent number
US07750040B2

Reaction notes

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