Benzamide → HCID 178457678, compound

HRID 1767676Notes

Reaction equation

HRID 1767676 reaction equation
[C:1]([NH2:9])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Li])[CH2:11][CH2:12][CH3:13].[Li].C[O:17][B:18](OC)[O:19]C.[CH2:23]1[CH2:27]OC[CH2:24]1>>[CH:12]([N:9]([CH:23]([CH3:27])[CH3:24])[C:1](=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)([CH3:13])[CH3:11].[BH:18]([OH:19])[OH:17]

Participants

6

Reactant 5

HCID 2331BenzamideHCID 8028TetrahydrofuranHCID 8470Trimethyl borateHCID 3028194LithiumHCID 178418339Butyllithium

Product 1

HCID 178457678HCID 178457678, compound

Procedure

Disopropyl benzamide (10.0 g, 48.7 mmol) was dissolved in 200 mL of dry THF. This reaction was placed under inert atmosphere and cooled to −78° C. n-Butyl lithium (20.5 mL, 2.5 M) was added dropwise over a 15 minute period. This reaction mixture was stirred at this temperature for 4 h with a noticeable precipitation of the lithium salt. Trimethoxyborane (5.8 mL, 51.2 mmol) was added dropwise over a 10 minute period and the reaction was warmed to room temperature and stirred overnight. The reaction mixture was poured onto 300 g of ice and allowed to warm to room temperature. This mixture was partitioned in a separatory funnel and the aqueous layer was extracted once with 100 mL of DCM. The organic layer was acidified with conc. HCl and extracted with DCM (3×100 mL). The combined organic layers were dried arid concentrated in vacuo. The residual foam was dried on high vac for several hours. The resulting material, 5.8 g (48%) was the desired product 2 as characterized spectroscopically (cis:tran amide): 1H NMR (CDCl3): δ 8.04 (d, 0.7H), 7.94 (d, 0.3H), 7.35 (m, 3H), 4.11 (m, 0.7H), 3.74 (m, 0.3H), 3.54 (m, 0.3H), 3.37 (m, 0.7H), 1.57 (d, 1.8H), 1.26 (m, 6H), 1.08 (d, 4.2H).

Workup

  1. additionwas added dropwise over a 15 minute period
  2. temperatureto warm to room temperature
  3. customThis mixture was partitioned in a separatory funnel
  4. extractionthe aqueous layer was extracted once with 100 mL of DCM
  5. extractionextracted with DCM (3×100 mL)
  6. customThe combined organic layers were dried arid
  7. concentrationconcentrated in vacuo
  8. customThe residual foam was dried on high vac for several hours

Sources & evidence

ORD record
ord-b2def989ed924afb923204c6cc7c66f0
Source dataset
uspto-grants-2007_06
Patent number
US07235557B2

Reaction notes

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