Sodium hydride → HCID 69031011, compound

HRID 489597Notes

Reaction equation

HRID 489597 reaction equation
[CH3:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6]Br)=[CH:4][C:3]=1[Br:10].[CH3:11][C:12]([O:15][C:16]([NH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])=[O:17])([CH3:14])[CH3:13].[H-].[Na+]>O1CCCC1>[C:22]([O:21][C:19]([N:18]([CH2:6][C:5]1[CH:8]=[CH:9][C:2]([CH3:1])=[C:3]([Br:10])[CH:4]=1)[C:16]([O:15][C:12]([CH3:14])([CH3:13])[CH3:11])=[O:17])=[O:20])([CH3:25])([CH3:24])[CH3:23]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 279800Di-tert-butyl IminodicarboxylateHCID 222661682-Bromo-4-(bromomethyl)-1-methylbenzene

Product 1

HCID 69031011HCID 69031011, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 4-methyl-3-bromobenzylbromide (1.63 g, 6.2 mmol, prepared according to the procedure described in International Patent Application No. WO 0009475) and di-tert-butyliminodicarboxylate (1.48 g, 6.8 mmol) in anhydrous tetrahydrofuran (15 ml) was treated portionwise with sodium hydride (0.27 g of 60% dispersion in mineral oil, 6.8 mmol). The mixture was stirred at ambient temperature for 18 hours then partitioned between saturated aqueous ammonium chloride solution (20 ml) and ethyl acetate (3 lots of 80 ml). The combined organic layers were washed with brine (80 ml), then dried over magnesium sulfate and concentrated under vacuum. The residue was subjected to chromatography on silica gel eluting with a mixture of cyclohexane and diethyl ether (9:1, v/v) to give 4-[N,N-bis-(tert-butoxycarbonyl)aminomethyl]-2-bromo-toluene as a pale yellow oil (2.4 g). 1H NMR (CDCl3, 500 MHz): δ 7.45 (s, 1H), 7.18 (m, 2H), 4.71 (s, 2H), 2.38 (s, 3H), 1.43 (s, 18H).

Workup

  1. customthen partitioned between saturated aqueous ammonium chloride solution (20 ml) and ethyl acetate (3 lots of 80 ml)
  2. washThe combined organic layers were washed with brine (80 ml)
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under vacuum
  5. additionThe residue was subjected to chromatography on silica gel eluting with a mixture of cyclohexane and diethyl ether (9:1

Sources & evidence

ORD record
ord-0e1e4e5ec3304ba59f151799de9edadb
Source dataset
uspto-grants-2005_12
Patent number
US06977263B2

Reaction notes

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