Bromoform → Methyl 2-((5-bromo-4-(4-cyclopropylnaphthalen-1-yl)-4H-1,2,4-triazol-3-yl)thio)acetate

HRID 38752

Reaction equation

HRID 38752 reaction equation
N([O-])=O.[Na+].N[C:6]1[N:7]([C:17]2[C:26]3[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=3)[C:20]([CH:27]3[CH2:29][CH2:28]3)=[CH:19][CH:18]=2)[C:8]([S:11][CH2:12][C:13]([O:15][CH3:16])=[O:14])=[N:9][N:10]=1.ClC(Cl)C(O)=O.ClCCl.C(Br)(Br)[Br:40]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1>[Br:40][C:6]1[N:7]([C:17]2[C:26]3[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=3)[C:20]([CH:27]3[CH2:29][CH2:28]3)=[CH:19][CH:18]=2)[C:8]([S:11][CH2:12][C:13]([O:15][CH3:16])=[O:14])=[N:9][N:10]=1

Participants

7

Reactant 5

HCID 5558BromoformHCID 6344DichloromethaneHCID 6597Dichloroacetic AcidHCID 23668193Sodium NitriteHCID 59763691Methyl 2-((5-amino-4-(4-cyclopropylnaphthalen-1-yl)-4H-1,2,4-triazol-3-yl)thio)acetate

Product 1

HCID 57811446Methyl 2-((5-bromo-4-(4-cyclopropylnaphthalen-1-yl)-4H-1,2,4-triazol-3-yl)thio)acetateYield 85%

Reagents, catalysts & solvents 1

HCID 66133Benzyl triethylammonium chlorideCatalyst

Procedure

Sodium nitrite (2.76 g, 40 mmol) was added to a solution of methyl 2-(5-amino-4-(1-cyclopropylnaphthalen-4-yl)-4H-1,2,4-triazol-3-ylthio)acetate (0.71 g, 2 mmol) and benzyltriethylammonium chloride (1.63 g, 6 mmol) in bromoform (10 mL). Dichloroacetic acid (0.33 mL, 4 mmol) was then added and the reaction mixture stirred at room temperature for 3 h. The mixture was directly loaded onto a 7-inch column of silica gel, packed with dichloromethane (DCM). The column was first eluted with DCM until all bromoform eluted, then eluted with acetone/DCM (5:95) to give methyl 2-(5-bromo-4-(1-cyclopropylnaphthalen-4-yl)-4H-1,2,4-triazol-3-ylthio)acetate (713 mg, 85%).

Workup

  1. washThe column was first eluted with DCM until all bromoform
  2. washeluted
  3. washeluted with acetone/DCM (5:95)

Sources & evidence

ORD record
ord-83895df429f74054be8d620d0aef6216
Source dataset
uspto-grants-2013_09
Patent number
US08524754B2

Linked notes

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