(5-Chlorothien-2-yl)tributyl tin → 2-Amino-6-methyl-5-(5-chlorothien-2-yl)benzonitrile

HRID 363777Notes

Reaction equation

HRID 363777 reaction equation
[Cl:1][C:2]1[S:6][C:5]([Sn](CCCC)(CCCC)CCCC)=[CH:4][CH:3]=1.[NH2:20][C:21]1[CH:28]=[CH:27][C:26](I)=[C:25]([CH3:30])[C:22]=1[C:23]#[N:24]>C1(C)C=CC=CC=1.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[CH:28]=[CH:27][C:26]([C:5]2[S:6][C:2]([Cl:1])=[CH:3][CH:4]=2)=[C:25]([CH3:30])[C:22]=1[C:23]#[N:24]

Participants

5

Reactant 2

HCID 11122380(5-Chlorothien-2-yl)tributyl tinHCID 534185926-Amino-3-iodo-2-methylbenzonitrile

Product 1

HCID 540460762-Amino-6-methyl-5-(5-chlorothien-2-yl)benzonitrileYield 53.6%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

A solution of 5.9 grams (0.015 mole) of (5-chlorothien-2-yl)tributyl tin and 3.0 grams (0.015 mole) of 2-amino-5-iodo-6-methylbenzonitrile in 150 mL of toluene was stirred, and 0.2 gram (catalyst) of tetrakis(triphenylphosphine)palladium(0) was added. The reaction vessel was evacuated, and then back-filled with dry nitrogen gas. This process was repeated two more times. The reaction mixture was then heated to reflux where it was stirred for about 18 hours. After this time the reaction mixture was concentrated under reduced pressure to a residue. The residue was dissolved in methylene chloride, and the solution was filtered through a fiber-glass pad to remove the catalyst. The filtrate was subjected to column chromatography on silica gel. Elution was accomplished using methylene chloride. The product-containing fractions were combined and concentrated under reduced pressure, yielding 2.0 grams of 2-amino-6-methyl-5-(5-chlorothien-2-yl)benzonitrile, mp 108°-110° C. The NMR spectrum was consistent with the proposed structure.

Workup

  1. customThe reaction vessel was evacuated
  2. additionback-filled with dry nitrogen gas
  3. temperatureThe reaction mixture was then heated
  4. temperatureto reflux where it
  5. concentrationAfter this time the reaction mixture was concentrated under reduced pressure to a residue
  6. dissolutionThe residue was dissolved in methylene chloride
  7. filtrationthe solution was filtered through a fiber-glass pad
  8. customto remove the catalyst
  9. washElution
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-5094436763d342d890ffd016244089df
Source dataset
uspto-grants-1999_02
Patent number
US05874579

Reaction notes

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