Hydrochloric Acid → (1S,5S)-1-(1-naphthyl)bicyclo[3.1.0]hexan-3-one

HRID 1096762Notes

Reaction equation

HRID 1096762 reaction equation
C1(S(C2(SC)[CH2:15][C@H:14]3[C@:12]([C:16]4[C:25]5[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=5)[CH:19]=[CH:18][CH:17]=4)([CH2:13]3)[CH2:11]2)(=O)=O)C=CC=CC=1.[CH3:28][OH:29].Cl>C(OCC)(=O)C.CCCCCC>[C:16]1([C@:12]23[CH2:13][C@H:14]2[CH2:15][C:28](=[O:29])[CH2:11]3)[C:25]2[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=2)[CH:19]=[CH:18][CH:17]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 887MethanolHCID 86622518(1S,5S)-3-Benzenesulfonyl-1-(1-naphthyl)-3-methylsulfanyl-bicyclo[3.1.0]hexane

Product 1

HCID 66781229(1S,5S)-1-(1-naphthyl)bicyclo[3.1.0]hexan-3-oneYield 99%

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent

Procedure

(1S,5S)-3-Benzenesulfonyl-1-(1-naphthyl)-3-methylsulfanyl-bicyclo[3.1.0]hexane (3 g, 7.6 mmol), methanol (18 mL) and concentrated hydrochloric acid (5.4 mL) were heated to reflux for 7 hours. The reaction was monitored by TLC (ethyl acetate/hexane (20:80)).The reaction mixture was concentrated under reduced pressure to remove methanol. The pH of the reaction mass was adjusted to 8-9 with saturated sodium bicarbonate solution. The aqueous layer was extracted with diethyl ether (300 mL). The organic layer was washed with water, dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to yield 3 g of crude oil, which was purified by preparative HPLC to give 1 g (62%) of 99% pure product. 1H NMR δ(300 MHz,CDCl3): 0.75-0.78 (1H,t, J=4 Hz), 1.37 (1H,m), 1.98-2.04 (1H,m), 2.49-2.55 (1H,d ,J=18 Hz), 2.77-2.79 (2H,d,J=6 Hz), 3.03-3.11 (2H,dd,J=18,6 Hz), 7.39-7.44 (1H,m), 7.48-7.57 (3H,m),7.76-7.78 (1H,d,J=6 Hz), 7.87-7.90 (1H,m), 8.12-8.15 (2H,d ,J=9 Hz).

Workup

  1. temperatureto reflux for 7 hours
  2. concentration80)).The reaction mixture was concentrated under reduced pressure
  3. customto remove methanol
  4. extractionThe aqueous layer was extracted with diethyl ether (300 mL)
  5. washThe organic layer was washed with water
  6. dry with materialdried over anhydrous sodium sulphate
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. customto yield 3 g of crude oil, which
  10. customwas purified by preparative HPLC

Sources & evidence

ORD record
ord-73541acc967146618797bc8f73b4db1c
Source dataset
uspto-grants-2012_03
Patent number
US08138377B2

Reaction notes

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