Water → HCID 178478455, compound

HRID 552594Notes

Reaction equation

HRID 552594 reaction equation
[ClH:1].Cl.[Br:3][C:4]1[CH:5]=[C:6]([NH2:11])[C:7]([NH2:10])=[CH:8][CH:9]=1.[C:12]1([C:18]#[C:19][C:20](O)=O)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.O.[OH-].[Na+]>C(O)CO>[Br:3][C:4]1[CH:9]=[CH:8][C:7]2[NH:10][C:20](/[CH:19]=[C:18](/[Cl:1])\[C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)=[N:11][C:6]=2[CH:5]=1

Participants

6

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 69475Phenylpropiolic AcidHCID 67164044HCID 67164044, compound

Product 1

HCID 178478455HCID 178478455, compound

Reagents, catalysts & solvents 1

HCID 174Ethylene GlycolSolvent

Procedure

A mixture of 4-bromo-benzene-1,2-diamine dihydrochloride (1.3 g, 5 mmol), phenylpropiolic acid (0.73 g, 5 mmol) in 4 mL of ethylene glycol was heated to reflux for 5 h. The mixture was cooled to rt and poured into water. The mixture was neutralized with 2N sodium hydroxide and filtered. The solid was suspended in water and extracted with ethyl acetate. The organic layers were combined, dried with anhydrous sodium sulfate, and filtered. The filtrate was concentrated to yield a red oil. The residue was purified using preative TLC plates twice (silica gel, 20×20 cm, 2000 microns, EtOAc:hexanes 3:7 and silica gel, 20×20 cm, 2000 microns, EtOAc:dichloromethane 3:97) to provide a mixture of cis and trans isomers of the title Compound 30a (0.345 g). 1H NMR (400 MHz, DMSO-d6) δ (ppm): 12.59 (m, 1H), 7.86-7.78 (m, 3H), 7.64-7.56 (m, 1H), 7.54-7.49 (m, 3H), 7.46 (s, 1H), 7.40-7.34 (m, 1H). Mass Spectrum (LCMS, APCl pos.) Calcd. For C15H10BrClN2:333.0 (M+H), Found 333.1.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 5 h
  3. filtrationfiltered
  4. extractionextracted with ethyl acetate
  5. dry with materialdried with anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated
  8. customto yield a red oil
  9. customThe residue was purified
  10. customto provide

Sources & evidence

ORD record
ord-2a711dfa3eaf49b28f7a2c7c545d3b08
Source dataset
uspto-grants-2011_05
Patent number
US07951829B2

Reaction notes

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