Ammonia → HCID 135786532, compound

HRID 1493020Notes

Reaction equation

HRID 1493020 reaction equation
C([Li])CCC.[NH3:6].[NH2-].[Li+].[CH3:9][C:10]([C:13]1[CH:14]=[C:15]([C:24]2[S:28][C:27]([C:29]([O:31]C)=O)=[N:26][N:25]=2)[CH:16]=[C:17]([C:20]([CH3:23])([CH3:22])[CH3:21])[C:18]=1[OH:19])([CH3:12])[CH3:11]>CCCCCC.O1CCCC1>[CH3:21][C:20]([C:17]1[CH:16]=[C:15]([C:24]2[S:28][C:27]([C:29]([NH2:6])=[O:31])=[N:26][N:25]=2)[CH:14]=[C:13]([C:10]([CH3:11])([CH3:12])[CH3:9])[C:18]=1[OH:19])([CH3:22])[CH3:23]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 24532Lithium amideHCID 136403398HCID 136403398, compoundHCID 178418339Butyllithium

Product 1

HCID 135786532HCID 135786532, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

A solution of 2.0 ml (3.20 mmol) of 1.6M n-butyllithium in hexane is added dropwise to liquid ammonia (3-5 ml) at -78° C. over 10 minutes under a nitrogen atmosphere. The resulting white slurry is treated slowly with 10 ml of tetrahydrofuran and the resulting mixture of lithium amide at -78° C. is treated dropwise with a solution of 1.08 g (3.10 mmol) of 5-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1,3,4-thiadiazole-2-carboxylic acid, methyl ester in 3 ml of tetrahydrofuran. The reaction is allowed to warm slowly to room temperature and stirred for a total of 18 hours. The reaction is quenched with 100 ml of saturated aqueous NH4Cl and extracted with t-butylmethylether (3×). The combined organic extracts are washed with brine, dried over Na2SO4, and concentrated in vacuo to give a yellow solid. Chromatography (flash, SiO2, 70-230 mesh, 30% ethyl acetate-hexane) followed by recrystallization from toluene gives 0.68 g (1.03 g theor., 66%) of the desired product as a pale yellow solid, mp 200°-201° C.

Workup

  1. customThe reaction is quenched with 100 ml of saturated aqueous NH4Cl
  2. extractionextracted with t-butylmethylether (3×)
  3. washThe combined organic extracts are washed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated in vacuo
  6. customto give a yellow solid
  7. customChromatography (flash, SiO2, 70-230 mesh, 30% ethyl acetate-hexane) followed by recrystallization from toluene

Sources & evidence

ORD record
ord-8fbd64e9d0ac4da6a54399f29321a1c1
Source dataset
uspto-grants-1994_12
Patent number
US05376670

Reaction notes

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