Butylimidazole → 9-Cyano-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid ethyl ester

HRID 84635

Reaction equation

HRID 84635 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[S:7][C:8]2[CH2:9][CH2:10][O:11][C:12]3[CH:19]=[CH:18][C:17](Br)=[CH:16][C:13]=3[C:14]=2[N:15]=1)=[O:5])[CH3:2].[CH2:21]([N:25]1C=CN=C1)CCC>C1(C)C=CC=CC=1.[Fe-4](C#N)(C#N)(C#N)(C#N)(C#N)C#N.[K+].[K+].[K+].[K+].[Cu]I>[CH2:1]([O:3][C:4]([C:6]1[S:7][C:8]2[CH2:9][CH2:10][O:11][C:12]3[CH:19]=[CH:18][C:17]([C:21]#[N:25])=[CH:16][C:13]=3[C:14]=2[N:15]=1)=[O:5])[CH3:2]

Participants

6

Reactant 2

HCID 61347ButylimidazoleHCID 67050521Ethyl 9-bromo-4,5-dihydrobenzo[2,3]oxepino[4,5-D]thiazole-2-carboxylate

Product 1

HCID 668686059-Cyano-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid ethyl ester

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178511492HCID 178511492, compoundCatalystHCID 1140TolueneSolvent

Procedure

A mixture of 9-bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid ethyl ester (500 mg), potassium ferrocyanide (dried, 104 mg), copper (I) iodide (27 mg) and 1-butylimidazole (0.37 mL) in toluene (3 mL) was reacted in the microwave at 160° C. for 4 h. The mixture was then partitioned between dichloromethane (30 mL) and water (20 mL). The organic layer was dried (MgSO4), reduced in vacuo and purified on silica to give 9-cyano-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid ethyl ester.

Workup

  1. customwas reacted in the microwave at 160° C. for 4 h
  2. customThe mixture was then partitioned between dichloromethane (30 mL) and water (20 mL)
  3. dry with materialThe organic layer was dried (MgSO4)
  4. custompurified on silica

Sources & evidence

ORD record
ord-f93db726695745e9b2a4f1d416c38efe
Source dataset
uspto-grants-2014_09
Patent number
US08846762B2

Linked notes

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