N,N,N',N'-Tetramethylethylenediamine → 6-(2,5-dimethyl-1H-pyrrol-1-yl)-4-methyl-2-pyridinebutanamine

HRID 2180102Notes

Reaction equation

HRID 2180102 reaction equation
[CH3:1][C:2]1[N:3]([C:8]2[CH:13]=[C:12]([CH3:14])[CH:11]=[C:10]([CH3:15])[N:9]=2)[C:4]([CH3:7])=[CH:5][CH:6]=1.[NH2:16][C:17]1N=C(C)C=[C:19](C)[CH:18]=1.CN(CCN(C)C)C.[Li]CCCC.BrCCCN1[Si](C)(C)CC[Si]1(C)C.[Cl-].[NH4+]>C(OCC)C.CCCCCC>[CH3:7][C:4]1[N:3]([C:8]2[N:9]=[C:10]([CH2:15][CH2:19][CH2:18][CH2:17][NH2:16])[CH:11]=[C:12]([CH3:14])[CH:13]=2)[C:2]([CH3:1])=[CH:6][CH:5]=1

Participants

9

Reactant 6

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 215072-Amino-4,6-dimethylpyridineHCID 25517Ammonium ChlorideHCID 42924111-(3-Bromoprop-1-yl)-2,2,5,5-tetramethyl-1,2,5-azadisilolidineHCID 224907362-(2,5-Dimethyl-1H-pyrrol-1-yl)-4,6-dimethylpyridineHCID 178418339Butyllithium

Product 1

HCID 224907456-(2,5-dimethyl-1H-pyrrol-1-yl)-4-methyl-2-pyridinebutanamineYield 62%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Conditions

Temperature
-20 °C

Procedure

1 g (5 mmol) of 2-(2,5-dimethyl-1H-pyrrol-1-yl)-4,6-dimethylpyridine (prepared from the 6-amino-2,4-lutidine according to J. Chem. Soc., Perkin Trans., 1984, 12, 2801) is dissolved, under an argon atmosphere, in 10 ml of anhydrous ethyl ether and 1.132 ml (7.5 mmol) of N,N,N,N-tetramethylethylenediamine (TMEDA). The reaction mixture is cooled down to −20° C. and 2.4 ml (6 mmol) of a 2.5 M solution of BuLi in hexane is added dropwise. After 5 hours at −20° C., the reaction mixture is cooled down to −45° C. and 1.68 g (6 mmol) of 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane is added and the temperature is allowed to return to ambient temperature overnight. 50 ml of a saturated solution of ammonium chloride is added and the mixture is agitated for 2 hours at 25° C. The organic phase is decanted and washed successively with 40 ml of water and 40 ml of salt water, dried over magnesium sulphate, filtered and concentrated under vacuum. The residue obtained is purified on a silica column (eluent=dichloromethane with 5% ethanol) in order to produce a yellow oil with a yield of 62%.

Workup

  1. temperaturethe reaction mixture is cooled down to −45° C.
  2. waitto return to ambient temperature overnight
  3. customThe organic phase is decanted
  4. washwashed successively with 40 ml of water and 40 ml of salt water
  5. dry with materialdried over magnesium sulphate
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customThe residue obtained
  9. customis purified on a silica column (eluent=dichloromethane with 5% ethanol) in order
  10. customto produce a yellow oil with a yield of 62%

Sources & evidence

ORD record
ord-1960476f855a49909fba1f51b8c2b9c0
Source dataset
uspto-grants-2005_05
Patent number
US06887891B2

Reaction notes

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