Propyl mercaptan → HCID 53240556, compound

HRID 422157Notes

Reaction equation

HRID 422157 reaction equation
[H-].[Li+].CCCS.C[O:8][C:9]1[CH:26]=[CH:25][CH:24]=[C:23]2[C:10]=1[C@@:11]1([CH3:30])[C@H:20]([CH2:21][S:22]2)[C@:19]2([CH3:27])[C@H:14]([C:15]([CH3:29])([CH3:28])[CH2:16][CH2:17][CH2:18]2)[CH2:13][CH2:12]1>CN(P(N(C)C)(N(C)C)=O)C>[CH3:30][C@@:11]12[CH2:12][CH2:13][C@@H:14]3[C@:19]([CH3:27])([CH2:18][CH2:17][CH2:16][C:15]3([CH3:29])[CH3:28])[C@H:20]1[CH2:21][S:22][C:23]1[C:10]2=[C:9]([OH:8])[CH:26]=[CH:25][CH:24]=1

Participants

5

Reactant 3

HCID 7848Propyl mercaptanHCID 62714Lithium hydrideHCID 53240552HCID 53240552, compound

Product 1

HCID 53240556HCID 53240556, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent2×

Procedure

In a reaction vessel HMPA (5 mL) was placed and purged with nitrogen for 1 h. To the vessel LiH (0.137 g, 17.4 mmol) and n-propylthiol (1.65 mL, 18.3 mmol) were added and the mixture was stirred at room temperature for 30 min. A solution of (1R,10R,11S,16S)-3-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02, 7.011,16]octadeca-2,4,6-triene (Compound No. 52) (0.10 g, 0.29 mmol) in HMPA (5 mL) was added to the reaction mixture and heated at 130° C. for 1 h. The reaction was cooled to room temperature, quenched with water (50 mL) and extracted with EtOAc (3×200 mL). The organic layers were combined, dried (Na2SO4) and concentrated. Purification by column chromatography on silica gel (Hexanes/EtOAc, 10:1) gave (1R,10R,11S,16S)-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-ol (Compound No. 55) (0.09 g, 94%) as a white solid. 1H NMR (CDCl3): δ 6.81 (t, 1H), 6.63 (d, 1H), 6.28 (d, 1H), 4.70 (s, 1H), 3.38 (m, 1H), 2.82 (q, 2H), 1.90-1.40 (m, 9H), 1.38 (s, 3H), 1.36-0.98 (m, 2H), 0.95 (s, 3H), 0.88 (m, 3H), 0.85 (s, 3H).

Workup

  1. custompurged with nitrogen for 1 h
  2. temperatureheated at 130° C. for 1 h
  3. temperatureThe reaction was cooled to room temperature
  4. customquenched with water (50 mL)
  5. extractionextracted with EtOAc (3×200 mL)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. customPurification by column chromatography on silica gel (Hexanes/EtOAc, 10:1)

Sources & evidence

ORD record
ord-2b508fe5e80046f89610a78d4a0eef2c
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

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