Ammonium Chloride → HCID 21949964, compound

HRID 2215806Notes

Reaction equation

HRID 2215806 reaction equation
[C:1]([Si:5]([CH3:19])([CH3:18])[O:6][CH2:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[N+:15]([O-])=O)([CH3:4])([CH3:3])[CH3:2].[CH:20]([Mg]Br)=[CH2:21].[Cl-].[NH4+]>C1COCC1.CCOC(C)=O>[C:1]([Si:5]([CH3:19])([CH3:18])[O:6][CH2:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]2[C:10]=1[NH:15][CH:21]=[CH:20]2)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 12007215HCID 12007215, compoundHCID 178418507HCID 178418507, compound2×

Product 1

HCID 21949964HCID 21949964, compoundYield 56%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-45 °C

Procedure

A solution of tert-butyl-dimethyl-[2-(2-nitro-phenyl)-ethoxy]-silane (85.6 g, 304 mmol) in THF (1 L) was cooled to −65° C. and a 1.0 M solution of vinyl magnesium bromide in THF (913 mL, 913 mmol) was introduced while maintaining a temperature below −60° C. The reaction was stirred for 15 minutes at −45° C., additional vinyl magnesium-bromide (152 mL, 152 mmol) was added and the reaction was stirred at −45° C. for 30 minutes. The cold reaction was poured into saturated aq ammonium chloride (800 mL) and diluted with EtOAc (500 mL). The two layers were separated and the aqueous layer was extracted with EtOAc(2×200 mL). The organic layers were combined, washed with brine (400 mL), dried (MgSO4), filtered and concentrated. Flash chromatography (95% hexane/EtOAc) gave the title compound (47.1 g, 56%) as a transparent brown oil. 1H NMR (400 MHz, DMSO-d6) −0.11 (s, 6H), 0.80 (s, 9H), 3.03 (t, J=6.8 Hz, 2H), 3.85 (t, J=6.8 Hz, 2H), 6.39 (dd, J=1.2, 3.2 Hz, 1H), 6.86–6.92 (m, 2H), 7.28 (dd, J=3, 3 Hz, 1H), 7.36 (dd, J=4.8, 4.8 Hz, 1H), 11.02 (br s, 1H). MS (electrospray, m/z) 276 (M++1).

Workup

  1. temperaturewhile maintaining a temperature below −60° C
  2. stirringthe reaction was stirred at −45° C. for 30 minutes
  3. customThe cold reaction
  4. customThe two layers were separated
  5. extractionthe aqueous layer was extracted with EtOAc(2×200 mL)
  6. washwashed with brine (400 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-6ffb1835a60b4ef0854c435038c1e7b3
Source dataset
uspto-grants-2006_09
Patent number
US07109229B2

Reaction notes

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