Dimethyl Sulfoxide → HCID 20540224, compound

HRID 333284Notes

Reaction equation

HRID 333284 reaction equation
[C:1]([C:3]1([C:14]2[CH:23]=[CH:22][C:21]3[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=3)[CH:15]=2)[CH2:8][CH:7](C(OC)=O)[C:6](=[O:13])[CH2:5][CH2:4]1)#[N:2].CS(C)=O.CCOC(C)=O.CCCCCCC>[Cl-].[Na+].O.O>[CH:15]1[C:16]2[C:21](=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH:22]=[CH:23][C:14]=1[C:3]1([C:1]#[N:2])[CH2:4][CH2:5][C:6](=[O:13])[CH2:7][CH2:8]1

Participants

6

Reactant 3

HCID 679Dimethyl SulfoxideHCID 21899848Ethylacetate heptaneHCID 58954846HCID 58954846, compound

Product 1

HCID 20540224HCID 20540224, compoundYield 63.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
135 °C

Procedure

A 12-L, four-neck flask equipped with a temperature probe, reflux condenser and overhead stirrer was charged with methyl 5-cyano-5-(naphthalen-2-yl)-2-oxocyclohexanecarboxylate (600 g, 1.9 mol), brine (1 L) and DMSO (6 L). The mixture was heated to 135° C. and stirred for 12 h. The progress of the reaction was monitored by TLC (2:3 EtOAc/Heptane). After 12 h, the reaction mixture was cooled to room temperature, diluted with water (6 L) and extracted twice with MTBE (5 L, 3 L). The combined organic phases were washed with brine (4×3 L), dried over MgSO4 and filtered. The filtrate was concentrated under reduced pressure at 40-45° C. to give a residue which was triturated with heptane/MTBE (1:1, 2 L). The resulting slurry was stirred for 2 h, filtered and dried under high vacuum for 12 h to yield the title compound (301 g, 62%) as an off-white solid. 1H NMR (DMSO-d6, 300 MHz): 6 8.1 (s, 1H), 8.0-7.9 (m, 4H), 7.8 (dd, 1H), 7.6 (m, 2H), 7.3 (dd, 1H), 7.2 (m, 1H), 3.1 (s, 1H), 2.8 (m, 2H), 2.2-2.6 (m, 8H), 1.2(s, 2H).

Workup

  1. temperaturereflux condenser and overhead stirrer
  2. waitAfter 12 h
  3. temperaturethe reaction mixture was cooled to room temperature
  4. extractionextracted twice with MTBE (5 L, 3 L)
  5. washThe combined organic phases were washed with brine (4×3 L)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated under reduced pressure at 40-45° C.
  9. customto give a residue which
  10. customwas triturated with heptane/MTBE (1:1, 2 L)
  11. stirringThe resulting slurry was stirred for 2 h
  12. filtrationfiltered
  13. customdried under high vacuum for 12 h

Sources & evidence

ORD record
ord-6e6303ff8a724856953ebec3dadf2d5f
Source dataset
uspto-grants-2014_11
Patent number
US08877975B2

Reaction notes

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