Trimethyl((tributylstannyl)ethynyl)silane → HCID 90408305, compound

HRID 516581Notes

Reaction equation

HRID 516581 reaction equation
[CH3:1][Si:2]([CH3:19])([CH3:18])[C:3]#[C:4][Sn](CCCC)(CCCC)CCCC.[NH2:20][C:21]1[C:26]([F:27])=[C:25]([C:28]2[CH:33]=[CH:32][C:31](I)=[CH:30][CH:29]=2)[N:24]=[C:23]([C:35]([O:37][CH3:38])=[O:36])[C:22]=1[Cl:39]>CN(C)C=O.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>[NH2:20][C:21]1[C:26]([F:27])=[C:25]([C:28]2[CH:33]=[CH:32][C:31]([C:4]#[C:3][Si:2]([CH3:1])([CH3:18])[CH3:19])=[CH:30][CH:29]=2)[N:24]=[C:23]([C:35]([O:37][CH3:38])=[O:36])[C:22]=1[Cl:39]

Participants

6

Reactant 2

HCID 639663Trimethyl((tributylstannyl)ethynyl)silaneHCID 90409982HCID 90409982, compound

Product 1

HCID 90408305HCID 90408305, compoundYield 73%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

Trimethyl((tributylstannyl)ethynyl)silane (510 mg, 1.3 mmol, 1.1 equiv) was added to a stirred mixture of methyl 4-amino-3-chloro-5-fluoro-6-(4-iodophenyl)picolinate (490 mg, 1.2 mmol, 1.0 equiv) and tetrakis(triphenylphosphine)palladium(0) (140 mg, 0.12 mmol, 0.10 equiv) in N,N-dimethylformamide (2.4 mL) at 23° C. The reaction mixture was heated to 90° C., resulting in a homogeneous yellow solution, and stirred for 20 h. The cooled reaction mixture was diluted with water (200 mL) and extracted with diethyl ether (4×100 mL). Hexanes (100 mL) was added to the combined organic layers and the turbid solution was washed with water (200 mL). The organic layer was dried (magnesium sulfate), gravity filtered, and concentrated by rotary evaporation. The residue was purified by silica gel column chromatography (25% ethyl acetate in hexanes) to afford the title compound as a tan powder (330 mg, 73%): mp 83-86° C.; IR (thin film) 3487 (m), 3375 (s), 2958 (s), 2159 (m), 1739 (s), 1618 (s) cm−1; 1H NMR (300 MHz, CDCl3) δ 7.89 (m, 2H), 7.55 (m, 2H), 4.89 (br s, 2H), 3.99 (s, 3H), 0.26 (s, 9H); ESIMS m/z 377 ([M+H]+).

Workup

  1. customresulting in a homogeneous yellow solution
  2. customThe cooled reaction mixture
  3. extractionextracted with diethyl ether (4×100 mL)
  4. additionHexanes (100 mL) was added to the combined organic layers
  5. washthe turbid solution was washed with water (200 mL)
  6. dry with materialThe organic layer was dried (magnesium sulfate), gravity
  7. filtrationfiltered
  8. concentrationconcentrated by rotary evaporation
  9. customThe residue was purified by silica gel column chromatography (25% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-f52efc7b75454131a8a8749944cca95e
Source dataset
uspto-grants-2015_08
Patent number
US09113629B2

Reaction notes

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