Hexamethyldisilazane → HCID 53248106, compound

HRID 1914445Notes

Reaction equation

HRID 1914445 reaction equation
[C:1]([CH2:4][CH:5]([S:15]([OH:18])(=[O:17])=[O:16])[CH2:6][NH:7][C:8](=[O:14])/[CH:9]=[CH:10]\[C:11]([OH:13])=O)([OH:3])=[O:2].CC(N(C)C)=O.C[Si](N[Si](C)(C)C)(C)C>[Cl-].[Cl-].[Zn+2].C1(C)C=CC=CC=1>[O:13]=[C:11]1[CH:10]=[CH:9][C:8](=[O:14])[N:7]1[CH2:6][CH:5]([S:15]([OH:18])(=[O:17])=[O:16])[CH2:4][C:1]([OH:3])=[O:2]

Participants

6

Reactant 3

HCID 13838HexamethyldisilazaneHCID 31374DimethylacetamideHCID 53248105HCID 53248105, compound

Product 1

HCID 53248106HCID 53248106, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 1140TolueneSolvent

Procedure

(Z)-4-(3-carboxy-2-sulfopropylamino)-4-oxobut-2-enoic acid (450 mg, 1.60 mmol) in mixture of 10 ml of dry DMA and 50 ml of dry toluene was heated. After the temperature reached at 80° C., HMDS (hexamethyldisilazane, 1.80 ml, 8.63 mmol,) and ZnCl2 (3.2 ml, 1.0 M in diethyl ether) were added. The mixture was continued heated to 115˜125° C. and toluene was collected through Dean-Stark trap. The reaction mixture was fluxed at 120° C. for 6 h. During this period, 2×20 ml of dry toluene was added to keep the mixture volume around 8˜10 ml. Then the mixture was cooled, 1 ml of 1:10 HCl (conc)/CH3OH was added, evaporated, purified on SiO2 chromatography eluted with 1:5:0.01 CH3OH/CH2Cl2/HAc to afford 315 mg (75%) of the title product. 1H NMR (DMF-d7) 6.96 (s, 2H), 4.04 (dd, 1H, J=4.3, 13.8 Hz), 3.47 (m, 1H), 3.23 (dd, 1H, J=7.4, 14.7 Hz), 2.99 (dd, 1H, J=3.3, 16.8 Hz), 2.35 (dd, 1H, J=8.1, 16.9 Hz); 13C NMR 173.58, 172.18, 135.54, 54.61, 40.24, 32.43, ESI MS m/z− 261.70 (M−H).

Workup

  1. temperaturewas heated
  2. customreached at 80° C.
  3. temperatureThe mixture was continued heated to 115˜125° C.
  4. customtoluene was collected through Dean-Stark trap
  5. waitDuring this period
  6. addition2×20 ml of dry toluene was added
  7. temperatureThen the mixture was cooled
  8. addition1 ml of 1:10 HCl (conc)/CH3OH was added
  9. customevaporated
  10. custompurified on SiO2 chromatography
  11. washeluted with 1:5:0.01 CH3OH/CH2Cl2/HAc

Sources & evidence

ORD record
ord-90f3b420f45f45e2b525d8e3939166c7
Source dataset
uspto-grants-2013_12
Patent number
US08613930B2

Reaction notes

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