Triethylamine → HCID 22329720, compound

HRID 586213Notes

Reaction equation

HRID 586213 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([C:7]2[CH:15]=[CH:14][C:10]([C:11]([OH:13])=O)=[CH:9][CH:8]=2)=[CH:3][CH:2]=1.C(Cl)(=O)C(Cl)=O.[OH:22][CH2:23][CH:24]1[CH2:29][N:28]([S:30]([C:33]2[CH:42]=[CH:41][C:40]3[C:35](=[CH:36][CH:37]=[C:38]([Br:43])[CH:39]=3)[CH:34]=2)(=[O:32])=[O:31])[CH2:27][CH2:26][NH:25]1.C(N(CC)CC)C>ClCCl.O.CN(C=O)C>[Br:43][C:38]1[CH:39]=[C:40]2[C:35](=[CH:36][CH:37]=1)[CH:34]=[C:33]([S:30]([N:28]1[CH2:27][CH2:26][N:25]([C:11](=[O:13])[C:10]3[CH:9]=[CH:8][C:7]([C:4]4[CH:3]=[CH:2][N:1]=[CH:6][CH:5]=4)=[CH:15][CH:14]=3)[CH:24]([CH2:23][OH:22])[CH2:29]1)(=[O:32])=[O:31])[CH:42]=[CH:41]2

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 65578Oxalyl chloride2×HCID 15208114-(Pyridin-4-yl)benzoic acidHCID 22329739HCID 22329739, compound

Product 1

HCID 22329720HCID 22329720, compoundYield 56.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

A stirred suspension of 4-(4-pyridyl)benzoic acid (sodium salt) (190 mg, 0.86 mmol) in dichloromethane (10 ml) was treated with oxalyl chloride (0.2 ml, 2.3 mmol) and DMF (catalytic amount). After stirring for 2 hours, further oxalyl chloride 0.2 ml, 2.3 mmol) and DMF (catalytic amount) was added and the suspension stirred a further 4 hours. The solvent was removed in vacuo and the residue, after drying, was suspended in dichloromethane (20 ml) and treated with 2-(hydroxymethyl)-4-(6-bromonaphth-2-ylsulphonyl)piperazine (300 mg, 0.78 mmol) and triethylamine (0.36 ml, 2.5 mmol). After stirring at room temperature overnight the reaction mixture was diluted with dichloromethane (20 ml) and water (20 ml). A copious precipitate appeared which was filtered off, dried and recrystallised from ethyl acetate (10 ml) to yield 1-(6-bromonaphth-2-ylsulphonyl)-3-(hydroxymethyl)-4-[4-(4-pyridyl)benzoyl] piperazine as a colourless solid (250 mg); 1H NMR (300 MHz, DMSO-d6) δ=3-4 ppm (broad, 9H), δ7.2 ppm (d, 2H), δ=7.7 ppm (d, 2H), δ=7.8 ppm (m, 4H), δ=8.2 ppm (t, 2H), δ8.4 ppm (s,1H), δ=8.45 ppm (s,1H), δ=8.6 ppm (d, 2H); signals due ethyl acetate (1 mol eq) were also present; MS: (M+H)+ 566/568 (1 Br pattern); analysis; found: C, 56.8; H, 4.9; N, 6.3%; C27H24BrN3SO4. C4H8O2 requires: C, 56.9; H, 4.9; H, 4.9; N, 6.4%.

Workup

  1. stirringthe suspension stirred a further 4 hours
  2. customThe solvent was removed in vacuo
  3. customthe residue, after drying
  4. stirringAfter stirring at room temperature overnight the reaction mixture
  5. filtrationwas filtered off
  6. customdried
  7. customrecrystallised from ethyl acetate (10 ml)

Sources & evidence

ORD record
ord-f7240c32783a4ccfa5aba91c88245ba0
Source dataset
uspto-grants-2005_08
Patent number
US06936610B2

Reaction notes

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