Benzoyl chloride → HCID 90411254, compound

HRID 1754622Notes

Reaction equation

HRID 1754622 reaction equation
[C:1]([Si:5]([CH3:31])([CH3:30])[O:6][CH2:7][C@H:8]([CH2:19][N:20]1[CH:28]=[N:27][C:26]2[C:21]1=[N:22][CH:23]=[N:24][C:25]=2[NH2:29])[C@H:9]([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])[CH3:10])([CH3:4])([CH3:3])[CH3:2].[C:32](Cl)(=[O:39])[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1.N.CO>N1C=CC=CC=1>[C:1]([Si:5]([CH3:31])([CH3:30])[O:6][CH2:7][C@H:8]([CH2:19][N:20]1[CH:28]=[N:27][C:26]2[C:21]1=[N:22][CH:23]=[N:24][C:25]=2[NH:29][C:32](=[O:39])[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C@H:9]([O:11][Si:12]([C:15]([CH3:17])([CH3:18])[CH3:16])([CH3:13])[CH3:14])[CH3:10])([CH3:2])([CH3:3])[CH3:4]

Participants

5

Reactant 3

HCID 7412Benzoyl chlorideHCID 21705897Ammonia methanolHCID 90411445HCID 90411445, compound

Product 1

HCID 90411254HCID 90411254, compoundYield 74%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To a cold (˜0 C, ice/water bath) solution of 50 (2.65 g, 5.7 mmol) in 50 ml of anhydrous pyridine was added dropwise with stirring 1.0 ml (8.6 mmol) of benzoyl chloride (via a syringe). The reaction was allowed to warm up to room temperature, stirred for about 5 hrs until no starting material was found by HPLC analysis, and then treated with 10 ml of 6M NH3/MeOH. After being stirred for about 3 hrs and no more of the bis-benzoylated intermediate found by HPLC, the reaction was concentrated, re-suspended in dichloromethane (˜50 ml) and filtered to remove poorly insoluble benzamide. The filtrate was concentrated, washed with 10% citric acid, saturated NaCl, dried over Na2SO4 and concentrated again. The crude product was crystallized from 50% ethyl acetate/hexane (˜20 ml) to afford 2.4 g (74%) of 51 as white crystals. 1H NMR (DMSO-d6): δ 11.15 (s, 1H), 8.70 (s, 1H), 8.40 (s, 1H), 8.02 (d, J=7.2 Hz, 2H), 7.63 (m, 1H), 7.54 (t, J=7.8 Hz, 2H), 4.33 (m, 1H), 4.21 (m, 1H), 4.04 (m, 1H), 3.58 (m, 2H), 2.38 (m, 1H), 1.19 (d, J=6 Hz, 3H), 0.84 (s, 9H), 0.79 (s, 9H), 0.01 (s, 3H), 0.00 (s, 3H), −0.10 (s, 6H).

Workup

  1. stirringAfter being stirred for about 3 hrs
  2. concentrationthe reaction was concentrated
  3. filtrationfiltered
  4. customto remove poorly insoluble benzamide
  5. concentrationThe filtrate was concentrated
  6. washwashed with 10% citric acid, saturated NaCl
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated again
  9. customThe crude product was crystallized from 50% ethyl acetate/hexane (˜20 ml)

Sources & evidence

ORD record
ord-a7de5d764fa243e7b431c3c8a22155f4
Source dataset
uspto-grants-2015_10
Patent number
US09169256B2

Reaction notes

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