Acetic Acid → 6-({4-[(4-chlorophenyl)ethynyl]benzyl}amino)-2,2-dimethyl-4H-1,3-benzodioxin-4-one

HRID 551945Notes

Reaction equation

HRID 551945 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]#[C:9][C:10]2[CH:15]=[CH:14][C:13](/[CH:16]=[N:17]/[C:18]3[CH:30]=[CH:29][C:21]4[O:22][C:23]([CH3:28])([CH3:27])[O:24][C:25](=[O:26])[C:20]=4[CH:19]=3)=[CH:12][CH:11]=2)=[CH:4][CH:3]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(O)(=O)C>ClCCCl.O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]#[C:9][C:10]2[CH:15]=[CH:14][C:13]([CH2:16][NH:17][C:18]3[CH:30]=[CH:29][C:21]4[O:22][C:23]([CH3:28])([CH3:27])[O:24][C:25](=[O:26])[C:20]=4[CH:19]=3)=[CH:12][CH:11]=2)=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 5049666Sodium triacetoxyborohydrideHCID 178431704HCID 178431704, compound

Product 1

HCID 111543016-({4-[(4-chlorophenyl)ethynyl]benzyl}amino)-2,2-dimethyl-4H-1,3-benzodioxin-4-oneYield 93.4%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 962WaterSolvent

Procedure

A solution of 6-[((E)-{4-[(4-chlorophenyl)ethynyl]phenyl}methylidene)amino]-2,2-dimethyl-4H-1,3-benzodioxin-4-one (3.73 g, 8.97 mmol), sodium triacetoxyborohydride (5.70 g, 26.9 mmol) and acetic acid (0.77 mL, 13.5 mmol) in anhydrous DCE (120 mL) was stirred for 48 hrs at rt. Then the reaction mixture was diluted with water (150 mL) and an aqueous saturated solution of NaHCO3 (100 mL) and extracted with DCM (250 mL and 100 mL). The combined organic layers were dried over MgSO4 and evaporated under reduced pressure. The residue was crystallized from a DCM/pentane solution. The solid was filtered, washed with pentane (2×) and dried under reduced pressure to give 3.50 g (93%) of the title compound as a yellow powder. HPLC, Rt: 5.0 min (purity: 98.1%). 1H NMR (CDCl3) δ: 7.51 (d, J=8.2 Hz, 2H), 7.46 (d, J=8.5 Hz, 2H), 7.34 (m, 4H), 7.18 (d, J=2.6 Hz, 1H), 6.86 (dd, J=8.8, 2.6 Hz, 1H), 6.81 (d, J=8.8 Hz, 1H), 4.35 (s, 2H), 4.21 (brs, 1H), 1.71 (s, 6H).

Workup

  1. extractionan aqueous saturated solution of NaHCO3 (100 mL) and extracted with DCM (250 mL and 100 mL)
  2. dry with materialThe combined organic layers were dried over MgSO4
  3. customevaporated under reduced pressure
  4. customThe residue was crystallized from a DCM/pentane solution
  5. filtrationThe solid was filtered
  6. washwashed with pentane (2×)
  7. customdried under reduced pressure

Sources & evidence

ORD record
ord-ecac5e0ac3754885b36f107b5e471f8b
Source dataset
uspto-grants-2011_05
Patent number
US07947851B2

Reaction notes

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