Acetic Acid → HCID 67264249, compound

HRID 1687957Notes

Reaction equation

HRID 1687957 reaction equation
[C:1](=[O:4])([O-])[O-].[CH3:5][O:6][C:7]1[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][C:10]2[NH:11][C:12](=[O:16])[CH2:13][NH:14][CH2:15][C:9]=2[CH:8]=1.[C:22](O)(=O)[CH3:23].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(O)(C(F)(F)F)=O.O.C(O)C>[CH3:5][O:6][C:7]1[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][C:10]2[NH:11][C:12](=[O:16])[CH2:13][N:14]([CH2:22][CH2:23][O:4][CH3:1])[CH2:15][C:9]=2[CH:8]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 19660Carbonate IonHCID 5049666Sodium triacetoxyborohydrideHCID 67264267HCID 67264267, compound

Product 1

HCID 67264249HCID 67264249, compoundYield 38%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 22392675Trifluoroacetic acid waterSolvent

Procedure

A solution of 1,1,2-(trimethoxy)ethane (2.0 g, 16.4 mmol) in TFA/H2O (5 mL, 1/1 vol.) was stirred for five minutes at 50° C. The mixture was cooled to room temperature and neutralized to pH 6-7 by the addition of microporous carbonate (MP-CO3) with stirring. This was filtered into a solution of 7-methoxy-8-nitro-1,3,4,5-tetrahydro-benzo[e][1,4]diazepin-2-one (375 mg, 1.58 mmol) in ethanol (40 mL). The MP-CO3 was washed further with ethanol (10 mL) into the reaction mixture. To this was added acetic acid (0.36 mL, 6.34 mmol) and the mixture was stirred for two hours at room temperature before being treated with sodium triacetoxyborohydride (2.0 g, 9.4 mmol) and stirred at room temperature for an additional 18 hours. The mixture was concentrated, dissolved in dichloromethane, washed with saturated aqueous sodium bicarbonate and brine, dried over magnesium sulfate, filtered and concentrated. Flash chromatography over silica gel (0-10% MeOH-EtOAc) gave 7-methoxy-4-(2-methoxy-ethyl)-8-nitro-1,3,4,5-tetrahydro-benzo[e][1,4]diazepin-2-one (175 mg, 38%); 1H NMR (400 MHz, DMSO-d6) δ 10.02 (s, 1H), 7.61 (s, 1H), 7.32 (s, 1H), 3.91 (s, 6H), 3.44 (t, J=6 Hz, 2H), 3.41 (s, 2H), 2.69 (t, J=6 Hz, 2H); MS (m/e) 296 (M+1).

Workup

  1. washThe MP-CO3 was washed further with ethanol (10 mL) into the reaction mixture
  2. stirringthe mixture was stirred for two hours at room temperature
  3. stirringstirred at room temperature for an additional 18 hours
  4. concentrationThe mixture was concentrated
  5. dissolutiondissolved in dichloromethane
  6. washwashed with saturated aqueous sodium bicarbonate and brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-12eebc01858a46cf87e25e21a84269fc
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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