Hydrochloric Acid → HCID 11441998, compound

HRID 239064Notes

Reaction equation

HRID 239064 reaction equation
[OH:1][CH2:2][C:3]([CH3:22])([CH3:21])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][C:9](=[O:20])[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]([CH3:19])([CH3:18])[CH2:16][OH:17].C[C:24]1[CH:29]=[CH:28][C:27](S(C[N+]#[C-])(=O)=O)=[CH:26]C=1.[H-].[Na+].Cl>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CS(C)=O.CCOCC.CO.O>[OH:17][CH2:16][C:15]([CH3:18])([C:19]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:24]=1)[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][C:9](=[O:20])[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][C:3]([CH3:22])([C:21]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[CH2:2][OH:1]

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 161915Tosylmethyl isocyanideHCID 11738551HCID 11738551, compound

Product 1

HCID 11441998HCID 11441998, compoundYield 56%

Reagents, catalysts & solvents 5

HCID 67553Tetrabutylammonium IodideCatalystHCID 679Dimethyl SulfoxideSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

In analogy to the procedure of 214g, to a solution of 207h (18.0 g, 63.1 mmol), tetrabutylammonium iodide (2.0 g, 5.4 mmol) and TosMIC (4.8 g, 24.6 mmol) in anhydrous DMSO (250 mL) and Et2O (80 mL) was added NaH (60% dispersion in mineral oil, 2.5 g, 62.5 mmol) while cooling with an ice bath under N2 atmosphere. After 24 h at room temperature, the mixture was hydrolyzed and worked up by extraction to give the crude intermediate (18.0 g) as a brown oil. This crude material was heated to reflux in methanol (300 mL), concd HCl (36 mL) and water (70 mL) for 3 h. Extractive workup and purification by flash chromatography (silica gel; hexanes/ethyl acetate/hexanes=10/1, 5/1, 2/1) yielded 214h (6.1 g, 56%) as a yellowish oil. 1H NMR (CDCl3): δ 7.32-7.19 (m, 10 H), 3.68 (d, 2 H, J=10.8), 3.50 (d, 2 H, J=10.8), 2.26 (t, 4 H, J=7.50 H), 1.88-1.42 (m, 10 H), 1.25 (s, 6 H), 1.22-0.85 (m, 8 H). 13C NMR (CDCl3): δ 211.68, 144.94, 128.56, 126.82, 126.23, 72.68, 43.50, 42.79, 38.42, 30.01, 23.74, 23.68, 21.62. HRMS (LSIMS, nba): Calcd for C29H43O3 (MH+): 439.3212, found: 439.3207. HPLC: 95.3% pure.

Workup

  1. temperaturewhile cooling with an ice bath under N2 atmosphere
  2. extractionworked up by extraction
  3. customto give the crude intermediate (18.0 g) as a brown oil
  4. customExtractive workup and purification by flash chromatography (silica gel; hexanes/ethyl acetate/hexanes=10/1, 5/1, 2/1)

Sources & evidence

ORD record
ord-6e68703a7add44c5a8fa20d386c6668b
Source dataset
uspto-grants-2014_02
Patent number
US08642653B2

Reaction notes

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