Diisopropylamine → HCID 131720026, compound

HRID 1781536Notes

Reaction equation

HRID 1781536 reaction equation
C([NH:4]C(C)C)(C)C.[Li]CCCC.[CH3:13][O:14][C:15]1[C:23]([CH3:24])=[C:22]2[C:18]([C:19](=[O:25])[O:20][CH2:21]2)=[C:17]([O:26][CH2:27][O:28][CH2:29][CH2:30][O:31][CH3:32])[C:16]=1[CH2:33]/[CH:34]=[C:35](\[CH3:38])/[CH2:36]Br.[NH4+].[Cl-].[C:41]([O:44][CH2:45][CH3:46])(=[O:43])[CH3:42]>C1COCC1.CN(P(N(C)C)(N(C)C)=O)C>[CH3:32][O:31][CH2:30][CH2:29][O:28][CH2:27][O:26][C:17]1[C:16]([CH2:33]/[CH:34]=[C:35](\[CH3:38])/[CH2:36][CH:42]([NH2:4])[C:41]([O:44][CH2:45][CH3:46])=[O:43])=[C:15]([O:14][CH3:13])[C:23]([CH3:24])=[C:22]2[C:18]=1[C:19](=[O:25])[O:20][CH2:21]2

Participants

8

Reactant 5

HCID 7912DiisopropylamineHCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 67019128(E)-4-(1,3-dihydro-6-methoxy-4-methoxyethoxymethoxy-7-methyl-3-oxoisobenzofuran-5-yl)-2-methylbut-2-enyl bromideHCID 178418339Butyllithium

Product 1

HCID 131720026HCID 131720026, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
0 °C

Procedure

Freshly distilled diisopropylamine (0.435 ml) was dissolved in THF (10 ml). The solution was cooled to 0° C. and n-BuLi (1.3 ml, 2.38M) was added. The mixture was stirred at 0° C. for 20 minutes. The ice-bath was replaced by a dry ice-acetone bath and a solution of ethyl benzylidine glycinate (0.445 g) in THF (2 ml) was added slowly at -78°. The resulting red solution was stirred at -78° C. for 40 minutes. This solution was then transferred via cannula to a solution of (E)-4-(1,3-dihydro-6-methoxy -4-methoxyethoxymethoxy-7-methyl-3-oxoisobenzofuran-5-yl)-2-methylbut2-enyl bromide (0.667 g) dissolved in THF (20 ml) and HMPA (2 ml). After stirring the mixture at -78° C. for 90 minutes, the reaction mixture was poured into a concentrated solution of NH4Cl, extracted with ethyl acetate (3×30 ml), and the combined organic layers were dried over Na2SO4 and evaporated to give a dark oil, which was passed through a column (silica gel, ethyl acetate) giving 0.443 g (63%) of ethyl (E)-6-(4-methoxyethoxymethoxy -1,3-dihydro-6-methoxy-7-methyl-3-oxoisobenzofuran-5-yl)-2-amino-4-methyl -4-hexenoate the product as a light yellow oil.

Workup

  1. stirringThe resulting red solution was stirred at -78° C. for 40 minutes
  2. stirringAfter stirring the mixture at -78° C. for 90 minutes
  3. extractionextracted with ethyl acetate (3×30 ml)
  4. dry with materialthe combined organic layers were dried over Na2SO4
  5. customevaporated
  6. customto give a dark oil, which

Sources & evidence

ORD record
ord-974ff8f64ce5424998e02f92638f72db
Source dataset
uspto-grants-1997_05
Patent number
US05633279

Reaction notes

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