Hydrochloric Acid → HCID 67275555, compound

HRID 1698496Notes

Reaction equation

HRID 1698496 reaction equation
[Mg].Br[C:3]1[CH:8]=[CH:7][C:6]([S:9][CH2:10][CH:11]2[CH2:13][CH2:12]2)=[CH:5][CH:4]=1.[CH3:14][C:15]([O:19][Si](C)(C)C)([CH3:18])[C:16]#[N:17].[BH4-].[Na+].Cl>C(OCC)C.CO.O>[NH2:17][CH:16]([C:3]1[CH:8]=[CH:7][C:6]([S:9][CH2:10][CH:11]2[CH2:13][CH2:12]2)=[CH:5][CH:4]=1)[C:15]([CH3:18])([OH:19])[CH3:14]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 4311764Sodium borohydrideHCID 5462224MagnesiumHCID 129247282-Methyl-2-[(trimethylsilyl)oxy]propanenitrileHCID 579566301-Bromo-4-[(cyclopropylmethyl)thio]benzene

Product 1

HCID 67275555HCID 67275555, compoundYield 53.2%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

To magnesium turnings (888 mg) in diethyl ether (60 mL) was added 1-bromo-4-[(cyclopropylmethyl)thio]benzene (8.4 g). The mixture was heated at reflux for 16 hrs, and then cooled to ambient temperature. A solution of 2-methyl-2-[(trimethylsilyl)oxy]propanenitrile (4.35 g) in diethyl ether (30 mL) was then added and this solution was stirred at ambient temperature for 7 h. Sodium borohydride (1.33 g) in methanol (30 mL) was then slowly added and the solution aged for 2 h Water (25 mL) was added followed by 1N hydrochloric acid (100 mL) and the mixture stirred for 1 h. The organic layer was extracted with a further portion of 1N hydrochloric acid (100 mL) and the acid extracts combined. These were then made basic with 4N sodium hydroxide solution and extracted with dichloromethane (2×100 mL). The organic extracts were dried (MgSO4) and concentrated to give the title compound as a yellow solid (3.7 g). 1H NMR (360 MHz, CDCl3): δ 7.22-7.34 (4H, m), 3.77 (1H, s), 2.85 (2H, d, J=7.0 Hz), 1.21 (3H, s), 1.09-1.03 (1H, m), 1.03 (3H, s), 0.57 (2H, q, J=5.1 Hz), 0.24 (2H, q, J=5.1 Hz); m/z 307 (M-16[NH2])+.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 16 hrs
  3. waitthe solution aged for 2 h
  4. stirringthe mixture stirred for 1 h
  5. extractionThe organic layer was extracted with a further portion of 1N hydrochloric acid (100 mL)
  6. extractionextracted with dichloromethane (2×100 mL)
  7. dry with materialThe organic extracts were dried (MgSO4)
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-5b47c3a86e0940eda1bb766fca9eca3d
Source dataset
uspto-grants-2012_04
Patent number
US08163956B2

Reaction notes

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