Sodium Carbonate → 3-Bromo-7-[(1e)-3,3-diethoxy-1-propenyl]thieno[3,2-c]pyridin-4-amine

HRID 2390632Notes

Reaction equation

HRID 2390632 reaction equation
[Br:1][C:2]1[C:6]2[C:7]([NH2:12])=[N:8][CH:9]=[C:10](I)[C:5]=2[S:4][CH:3]=1.[CH2:13]([O:15][CH:16]([O:28][CH2:29][CH3:30])/[CH:17]=[CH:18]/B1OC(C)(C)C(C)(C)O1)[CH3:14].C([O-])([O-])=O.[Na+].[Na+]>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[C:6]2[C:7]([NH2:12])=[N:8][CH:9]=[C:10](/[CH:18]=[CH:17]/[CH:16]([O:28][CH2:29][CH3:30])[O:15][CH2:13][CH3:14])[C:5]=2[S:4][CH:3]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 11065022(E)-2-(3,3-Diethoxyprop-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 184507913-Bromo-7-iodothieno[3,2-C]pyridin-4-amine

Product 1

HCID 184507743-Bromo-7-[(1e)-3,3-diethoxy-1-propenyl]thieno[3,2-c]pyridin-4-amineYield 75%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

A mixture of Example 21A (200 mg, 0.56 mmol), 2-[(1E)-3,3-diethoxy-1-propenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (175 mg, 0.67 mmol), Pd(PPh3)4 (40 mg, 0.03 mmol) and Na2CO3 (120 mg, 1.13 mmol) in 1,2-dimethoxyethane (10 mL) and water (5 mL) was heated in an 85° C. oil bath for 15 hours. The mixture was cooled to room temperature and concentrated under reduced pressure. The mixture was extracted with dichloromethane and the extract was dried (MgSO4), filtered, and concentrated. The residue was purified by flash column chromatography on silica gel to provide the desired product (150 mg, 75%). 1H NMR (DMSO-d6, 400 MHz) δ 8.02 (s, 1H), 7.88 (s, 1H), 6.74 (d, 1H), 6.09 (dd, 1H), 5.09 (d, 1H), 3.62 (m, 2H), 3.48 (m, 2H), 1.15 (t, 6H); MS m/e 357.1, 359.1 (M+H)+.

Workup

  1. concentrationconcentrated under reduced pressure
  2. extractionThe mixture was extracted with dichloromethane
  3. dry with materialthe extract was dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by flash column chromatography on silica gel

Sources & evidence

ORD record
ord-bed913c7cf524194979ba699a9e209de
Source dataset
uspto-grants-2012_09
Patent number
US08273736B2

Reaction notes

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