Pyridine → N-(2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4,5,6,7-tetrahydrobenzo[b]thiophene-2-carboxamide

HRID 1363488Notes

Reaction equation

HRID 1363488 reaction equation
[CH3:1][C:2]1[C:7]([B:8]2[O:12][C:11]([CH3:14])([CH3:13])[C:10]([CH3:16])([CH3:15])[O:9]2)=[CH:6][CH:5]=[CH:4][C:3]=1[NH2:17].N1C=CC=CC=1.[S:24]1[C:28]([C:29](Cl)=[O:30])=[CH:27][C:26]2[CH2:32][CH2:33][CH2:34][CH2:35][C:25]1=2>C(Cl)Cl>[CH3:1][C:2]1[C:7]([B:8]2[O:12][C:11]([CH3:13])([CH3:14])[C:10]([CH3:16])([CH3:15])[O:9]2)=[CH:6][CH:5]=[CH:4][C:3]=1[NH:17][C:29]([C:28]1[S:24][C:25]2[CH2:35][CH2:34][CH2:33][CH2:32][C:26]=2[CH:27]=1)=[O:30]

Participants

5

Reactant 3

HCID 1049PyridineHCID 64853624,5,6,7-Tetrahydro-benzo[b]thiophene-2-carbonyl chlorideHCID 467380052-Methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

Product 1

HCID 58729134N-(2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4,5,6,7-tetrahydrobenzo[b]thiophene-2-carboxamideYield 91.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2-Methyl-3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenylamine (7) (1.20 g, 5.16 mmol, 1.0 equiv) and pyridine (0.42 mL, 25.8 mmol) are dissolved in DCM (40 mL) at 0° C. under a nitrogen atmosphere. 4,5,6,7-Tetrahydro-benzo[b]thiophene-2-carbonyl chloride (8) (1.03 g, 5.16 mmol) is then added in portions over 5 min and allowed to react warming to RT over 60 min. All solvent is then removed under reduced pressure, and the resultant oil is reduced from toluene (3×20 mL) to remove residual pyridine. The residue is then dissolved in ethyl acetate and washed with sodium hydroxide (1N, 1×100 mL), then washed with saturated sodium chloride (1×100 mL) and dried over sodium sulfate. The solution is then filtered and concentrated under reduced pressure to give 4,5,6,7-tetrahydro-benzo[b]thiophene-2-carboxylic acid [2-methyl-3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amide (9) as an off-white solid (1.87 g).

Workup

  1. customto react
  2. customAll solvent is then removed under reduced pressure
  3. customto remove residual pyridine
  4. dissolutionThe residue is then dissolved in ethyl acetate
  5. washwashed with sodium hydroxide (1N, 1×100 mL)
  6. washwashed with saturated sodium chloride (1×100 mL)
  7. dry with materialdried over sodium sulfate
  8. filtrationThe solution is then filtered
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-e7fdc3016b83494aa6f9da5b797090e1
Source dataset
uspto-grants-2011_02
Patent number
US07884108B2

Reaction notes

Loading…