Acetonitrile → HCID 69266642, compound

HRID 902428Notes

Reaction equation

HRID 902428 reaction equation
C([Mg]Br)C.[CH:5]([NH:8]C(C)C)(C)[CH3:6].C(#N)C.[CH2:15]([O:22][C:23]1[CH:30]=[C:29]2[C:26]([CH2:27][C:28]2([S:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C:31]#[N:32])=[CH:25][C:24]=1[O:40][CH3:41])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>C(OCC)C.O1CCCC1>[NH2:32][C:31]([C:28]1([S:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[CH2:27][C:26]2[C:29]1=[CH:30][C:23]([O:22][CH2:15][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)=[C:24]([O:40][CH3:41])[CH:25]=2)=[CH:6][C:5]#[N:8]

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 7912DiisopropylamineHCID 21956489HCID 21956489, compoundHCID 178418443HCID 178418443, compound

Product 1

HCID 69266642HCID 69266642, compoundYield 57.8%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a stirred solution of ethylmagnesium bromide (3.0 mL of a 3M solution in diethyl ether, 9.0 mmol) in anhydrous tetrahydrofuran (10 mL) at 0° C. under nitrogen is added diisopropylamine (2.5 mL, 17.8 mmol). The mixture is stirred at 0° C. for 1 hour and acetonitrile (0.25 mL, 4.8 mmol) and a solution of 4-benzyloxy-3-methoxy-7-phenylsulfanylbicyclo[4.2.0]octa-1,3,5-triene-7-carbonitrile (0.83 g, 2.2 mmol) in anhydrous tetrahydrofuran (3 mL) are added successively, and the resulting mixture is stirred for an additional hour. The reaction is quenched with aqueous ammonium chloride and the product is extracted with ethyl acetate. The extract is washed with brine, dried over anhydrous sodium sulfate and evaporated to yield a solid. The crude product is purified by silica gel chromatography, utilizing a 9:1 to 4:1 gradient of hexane/ethyl acetate to yield 0.527 g of 3-amino-3-(4-benzyloxy-3-methoxy-7-phenylsulfanylbicyclo[4.2.0]octa-1,3,5-trien-7-yl)acrylonitrile as a white solid, mp 122-125° C.

Workup

  1. stirringthe resulting mixture is stirred for an additional hour
  2. customThe reaction is quenched with aqueous ammonium chloride
  3. extractionthe product is extracted with ethyl acetate
  4. washThe extract is washed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. customevaporated
  7. customto yield a solid
  8. customThe crude product is purified by silica gel chromatography

Sources & evidence

ORD record
ord-08e8dcd3e84143ad90da32cda766c5e1
Source dataset
uspto-grants-2008_04
Patent number
US07365197B2

Reaction notes

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