Triethylamine → tert-Butyl 4-(6-chloro-5-nitropyrimidin-4-yl)piperazine-1-carboxylate

HRID 864390Notes

Reaction equation

HRID 864390 reaction equation
[CH3:1][C:2]([CH3:13])([O:4][C:5]([N:7]1[CH2:12][CH2:11][NH:10][CH2:9][CH2:8]1)=[O:6])[CH3:3].[Cl:14][C:15]1[C:20]([N+:21]([O-:23])=[O:22])=[C:19](Cl)[N:18]=[CH:17][N:16]=1.C(N(CC)CC)C>ClCCl.C(=O)(O)[O-].[Na+]>[CH3:3][C:2]([CH3:13])([O:4][C:5]([N:7]1[CH2:8][CH2:9][N:10]([C:19]2[N:18]=[CH:17][N:16]=[C:15]([Cl:14])[C:20]=2[N+:21]([O-:23])=[O:22])[CH2:11][CH2:12]1)=[O:6])[CH3:1]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 203124,6-Dichloro-5-nitropyrimidineHCID 143452tert-Butyl piperazine-1-carboxylate

Product 1

HCID 21477639tert-Butyl 4-(6-chloro-5-nitropyrimidin-4-yl)piperazine-1-carboxylate

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 516892Sodium BicarbonateSolvent

Procedure

A solution of 1-[1,1-dimethylethoxycarbonyl]piperazine (1.88 g) in dichloromethane (30 ml) is added drop by drop over 1.5 hr to a solution of 4,6-dichloro-5-nitropyrimidine (1.94 g) and triethylamine (1.32 g) in dichloromethane (170 ml) at -78°. After stirring an additional hr at -78°, the reaction is diluted with aqueous sodium bicarbonate (10%). The phases are separated, the organic phase is concentrated to a liquid which solidified on standing at 20°-25°. The solid is dissolved in chloroform and flash chromatographed on silica gel eluting with methanol/chloroform (1/99), pooling and concentrating the appropriate fractions gives the title compound, Anal. Calc for C13H18N5ClO4 ; MW=343.77: C,45.42; H,5.28; N,20.37; Cl,10.31. Found: C,45.52; H,5.40; N,20.34; Cl,10.36.

Workup

  1. customThe phases are separated
  2. concentrationthe organic phase is concentrated to a liquid which
  3. customon standing at 20°-25°
  4. dissolutionThe solid is dissolved in chloroform
  5. customflash chromatographed on silica gel eluting with methanol/chloroform (1/99)
  6. concentrationconcentrating the appropriate fractions

Sources & evidence

ORD record
ord-9b168dbef0804ccda0391c3f42242c8f
Source dataset
uspto-grants-1996_10
Patent number
US05563142

Reaction notes

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